High-throughput printing of semiconductor precursor layer from inter-metallic microflake particles

ABSTRACT

Methods and devices are provided for high-throughput printing of semiconductor precursor layer from microflake particles. In one embodiment, the method comprises of transforming non-planar or planar precursor materials in an appropriate vehicle under the appropriate conditions to create dispersions of planar particles with stoichiometric ratios of elements equal to that of the feedstock or precursor materials, even after settling. In particular, planar particles disperse more easily, form much denser coatings (or form coatings with more interparticle contact area), and anneal into fused, dense films at a lower temperature and/or time than their counterparts made from spherical nanoparticles. These planar particles may be microflakes that have a high aspect ratio. The resulting dense film formed from microflakes is particularly useful in forming photovoltaic devices. In one embodiment, at least one set of the particles in the ink may be inter-metallic flake particles (microflake or nanoflake) containing at least one group IB-IIIA inter-metallic alloy phase.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority to U.S. ProvisionalApplication Ser. No. 60/950,596 filed Jul. 18, 2007. This application isa continuation-in-part of commonly-assigned, co-pending U.S. patentapplication Ser. Nos. 11/361,498 now abandoned, 11/361,521 nowabandoned, 11/361,497, and 11/362,266 now abandoned, all filed on Feb.23, 2006. This application is a continuation-in-part ofcommonly-assigned, co-pending application Ser. No. 11/395,426 filed onMar. 30, 2006. This application is a continuation-in-part ofcommonly-assigned, application Ser. No. 11/290,633 entitled“CHALCOGENIDE SOLAR CELLS” filed Nov. 29, 2005 now U.S. Pat. No.8,048,477 and Ser. No. 10/782,017, entitled “SOLUTION-BASED FABRICATIONOF PHOTOVOLTAIC CELL” filed Feb. 19, 2004 now U.S. Pat. No. 7,663,057and published as U.S. patent application publication 20050183767, theentire disclosures of which are incorporated herein by reference. Thisapplication is also a continuation-in-part of commonly-assigned, U.S.patent application Ser. No. 10/943,657, entitled “COATED NANOPARTICLESAND QUANTUM DOTS FOR SOLUTION-BASED FABRICATION OF PHOTOVOLTAIC CELLS”filed Sep. 18, 2004 now U.S. Pat. No. 7,306,823, the entire disclosuresof which are incorporated herein by reference. This application is alsoa continuation-in-part of commonly-assigned, U.S. patent applicationSer. No. 11/081,163, entitled “METALLIC DISPERSION”, filed Mar. 16, 2005now U.S. Pat. No. 7,604,843, the entire disclosures of which areincorporated herein by reference. This application is a alsocontinuation-in-part of commonly-assigned, co-pending U.S. patentapplication Ser. No. 10/943,685, entitled “FORMATION OF CIGS ABSORBERLAYERS ON FOIL SUBSTRATES”, filed Sep. 18, 2004. The entire disclosuresof all documents listed above are incorporated herein by reference forall purposes.

FIELD OF THE INVENTION

This invention relates generally to semiconductor films, and morespecifically, to the fabrication of solar cells that use semiconductorfilms based on IB-IIIA-VIA compounds.

BACKGROUND OF THE INVENTION

Solar cells and solar modules convert sunlight into electricity. Theseelectronic devices have been traditionally fabricated using silicon (Si)as a light-absorbing, semiconducting material in a relatively expensiveproduction process. To make solar cells more economically viable, solarcell device architectures have been developed that can inexpensivelymake use of thin-film, light-absorbing semiconductor materials such ascopper-indium-gallium-sulfo-di-selenide, Cu(In, Ga)(S, Se)₂, also termedCI(G)S(S). This class of solar cells typically has a p-type absorberlayer sandwiched between a back electrode layer and an n-type junctionpartner layer. The back electrode layer is often Mo, while the junctionpartner is often CdS. A transparent conductive oxide (TCO) such as zincoxide (ZnO_(x)) typically doped with aluminum is formed on the junctionpartner layer and is typically used as a transparent electrode.CIS-based solar cells have been demonstrated to have power conversionefficiencies exceeding 19%.

A central challenge in cost-effectively constructing a large-areacopper-indium-gallium-di-selenide (CIGS)-based solar cell or module isthat the elements of the CIGS layer must be within a narrowstoichiometric ratio on nano-, meso-, and macroscopic length scale inall three dimensions in order for the resulting cell or module to behighly efficient. Achieving precise stoichiometric composition overrelatively large substrate areas is, however, difficult usingtraditional vacuum-based deposition processes. For example, it isdifficult to deposit compounds and/or alloys containing more than oneelement by sputtering or evaporation. Both techniques rely on depositionapproaches that are limited to line-of-sight and limited-area sources,tending to result in poor surface coverage. Line-of-sight trajectoriesand limited-area sources can result in non-uniform three-dimensionaldistribution of the elements in all three dimensions and/or poorfilm-thickness uniformity over large areas. These non-uniformities canoccur over the nano-, meso-, and/or macroscopic scales. Suchnon-uniformity also alters the local stoichiometric ratios of theabsorber layer, decreasing the potential power conversion efficiency ofthe complete cell or module.

Alternatives to traditional vacuum-based deposition techniques have beendeveloped. In particular, production of solar cells on flexiblesubstrates using non-vacuum, semiconductor printing technologiesprovides a highly cost-efficient alternative to conventionalvacuum-deposited solar cells. For example, T. Arita and coworkers [20thIEEE PV Specialists Conference, 1988, page 1650] described a non-vacuum,screen printing technique that involved mixing and milling pure Cu, Inand Se powders in the compositional ratio of 1:1:2 and forming a screenprintable paste, screen printing the paste on a substrate, and sinteringthis film to form the compound layer. They reported that although theyhad started with elemental Cu, In and Se powders, after the milling stepthe paste contained the Cu—In—Se₂ phase. However, solar cells fabricatedfrom the sintered layers had very low efficiencies because thestructural and electronic quality of these absorbers was poor.

Screen-printed Cu—In—Se₂ deposited in a thin-film was also reported byA. Vervaet et al. [9th European Communities PV Solar Energy Conference,1989, page 480], where a micron-sized Cu—In—Se₂ powder was used alongwith micron-sized Se powder to prepare a screen printable paste. Layersformed by non-vacuum, screen printing were sintered at high temperature.A difficulty in this approach was finding an appropriate fluxing agentfor dense Cu—In—Se₂ film formation. Even though solar cells made in thismanner had poor conversion efficiencies, the use of printing and othernon-vacuum techniques to create solar cells remains promising.

There is a widespread notion in the field, and certainly in the CIGSnon-vacuum precursor field, that the most optimized dispersions andcoating contain spherical particles and that any other shape is lessdesirable in terms of dispersion stability and film packing,particularly when dealing with nanoparticles. Accordingly, the processesand theories that dispersion chemists and coating engineers are gearedtoward involve spherical particles. Because of the high mass density ofthe particles used in CIGS non-vacuum precursors, especially thoseincorporating pure metals, the use of spherical particles requires avery small size in order to achieve a well dispersed media. This thenrequires that each component be of similar size in order to maintaindesired stoichiometric ratios throughout the precursor layer and finalcompound film, since otherwise, large particles will settle first.Additionally, spheroids are thought to be useful to achieve high packingdensity on a packing unit/volume basis, but even at high density,spheres only contact at tangential points which represent a very smallfraction of interparticle surface area. Furthermore, minimalflocculation is desired to reduce clumping if good atomic mixing isdesired in the resulting film.

Due to the aforementioned issues, many experts in the non-vacuumprecursor CIGS community desire spherical nanoparticles in sizes thatare as small as they can achieve. Although the use of traditionalspherical nanoparticles is still promising, many fundamental challengesremain, such as the difficulty in obtaining small enough sphericalnanoparticles in high yield and low cost (especially from CIGS precursormaterials) or the difficulty in reproducibly obtaining high qualityfilms. Furthermore, the lower interparticle surface area at contactpoints between spheroidal particles may serve to impede rapid processingof these particles since the reaction dynamics depend in many ways onthe amount of surface area contact between particles.

SUMMARY OF THE INVENTION

Embodiments of the present invention address at least some of thedrawbacks set forth above. The present invention provides for the use ofnon-spherical particles in the formation of high quality precursorlayers which are processed into dense films. The resulting dense filmsmay be useful in a variety of industries and applications, including butnot limited to, the manufacture of photovoltaic devices and solar cells.More specifically, the present invention has particular application inthe formation of precursor layers for thin film solar cells. The presentinvention provides for more efficient and simplified creation of adispersion, and the resulting coating thereof. It should be understoodthat this invention is generally applicable to any processes involvingthe deposition of a material from a dispersion. At least some of theseand other objectives described herein will be met by various embodimentsof the present invention.

In one embodiment of the present invention, a method is provided fortransforming non-planar and/or planar precursor metals in an appropriatevehicle under the appropriate conditions to create dispersions of planarparticles with stoichiometric ratios of elements close or equal to thatof the feedstock or precursor metals, even after selective settling. Inparticular, planar particles described herein have been found to beeasier to disperse, form much denser coatings, and anneal into films ata lower temperature and/or time than their counterparts made fromspherical nanoparticles that have substantially similar composition butdifferent morphology. Additionally, even unstable dispersions usinglarge microflake particles that may require continuous agitation to staysuspended still create good coatings. In one embodiment of the presentinvention, a stable dispersion is one that remains dispersed for aperiod of time sufficient to allow a substrate to be coated. In oneembodiment, this may involve using agitation to keep particles dispersedin the dispersion. In other embodiments, this may include dispersionsthat settle but can be re-dispersed by agitation and/or other methodswhen the time for use arrives.

In another embodiment of the present invention, a method is providedthat comprises of formulating an ink of particles wherein substantiallyall of the particles are microflakes. In one embodiment, at least about95% of all particles (based on total weight of all particles) aremicroflakes. In one embodiment, at least about 99% of all particles(based on total weight of all particles) are microflakes. In oneembodiment, all particles are microflakes. In yet another embodiment,all particles are microflakes and/or nanoflakes. Substantially each ofthe microflakes contains at least one element from group IB, IIIA and/orVIA, wherein overall amounts of elements from group IB, IIIA and/or VIAcontained in the ink are such that the ink has a desired or close to adesired stoichiometric ratio of the elements for at least the elementsof group IB and IIIA. The method includes coating a substrate with theink to form a precursor layer and processing the precursor layer in asuitable atmosphere to form a dense film. The dense film may be used inthe formation of a semiconductor absorber for a photovoltaic device. Thefilm may comprise of a partially or fully fused version of the precursorlayer which comprises of a plurality of individual particles which areunfused.

In yet another embodiment of the present invention, a material isprovided that comprises of a plurality of microflakes having a materialcomposition containing at least one element from Groups IB, IIIA, and/orVIA. The microflakes are created by milling or size reducing precursorparticles characterized by a precursor composition that providessufficient malleability to form a planar shape from a non-planar and/orplanar starting shape when milled or size reduced, and wherein overallamounts of elements from Groups IB, IIIA and/or VIA contained in theprecursor particles combined are at a desired or close to a desiredstoichiometric ratio of the elements for at least the elements of groupsIB and IIIA. In one embodiment, planar includes those that particlesthat are wide in two dimensions, thin in every other dimension. The sizereductionmilling may transform substantially all of the precursorparticles into microflakes. Alternatively, the size reduction millingtransforms at least about 50% of the precursor particles intomicroflakes. The milling may occur in an oxygen-free atmosphere tocreate oxygen-free microflakes. The milling may occur in an inert gasenvironment to create oxygen-free microflakes. The size reduction mayoccur in a reducing gas environment to ensure oxygen-free microflakes.The size reduction may occur in the presence of a stabilizer or reducingagent in the within the suspension to prevent or reverse oxidation.Milling can also be chilled and occur at a temperature lower than roomtemperature to allow milling of particles composed of low melting pointmaterial. In other embodiments, milling may occur at room temperature.Alternatively, milling may occur at temperatures greater than roomtemperature to obtain the desired malleability of the material. In oneembodiment of the present invention, the material composition of thefeedstock particles preferably exhibits a malleability that allowsnon-planar feedstock particles to be formed into substantially planarmicroflakes at the appropriate temperature. In one embodiment, themicroflakes have at least one surface that is substantially flat.

In a still further embodiment according to the present invention, asolar cell is provided that comprises of a substrate, a back electrodeformed over the substrate, a p-type semiconductor thin film formed overthe back electrode, an n-type semiconductor thin film formed so as toconstitute a pn junction with the p-type semiconductor thin film, and atransparent electrode formed over the n-type semiconductor thin film.The p-type semiconductor thin film results by processing a dense filmformed from a plurality of microflakes having a material compositioncontaining at least one element from Groups IB, IIIA, and/or VIA,wherein the dense film has a void volume of 26% or less. In oneembodiment, this number may be based on free volume of packed spheres ofdifferent diameter to minimize void volume. In another embodiment of theinvention, the dense film has a void volume of about 30% or less.

In another embodiment of the present invention, a method is provided forforming a film by using particles with particular properties. Theproperties may be based on particle size, shape, composition, andmorphology distribution. As a nonlimiting example, the particles may bemicroflakes within a desired size range. Within the microflakes, themorphology may include particles that are amorphous, those that arecrystalline, those that are more crystalline than amorphous, and thosethat are more amorphous than crystalline. The properties may also bebased on interparticle composition and morphology distribution. In oneembodiment of the present invention, it should be understood that theresulting flakes have a morphology where the flakes are less crystallinethan the feedstock material from which the flakes are formed.

In yet another embodiment of the present invention, the method comprisesformulating an ink of particles wherein about 50% or more of theparticles (based on the total weight of all particles) are flakes eachcontaining at least one element from group IB, IIIA and/or VIA andhaving a non-spherical, planar shape, wherein overall amounts ofelements from group IB, IIIA and/or VIA contained in the ink are suchthat the ink has a desired stoichiometric ratio of the elements. Inanother embodiment, 50% or more may be based on the number of particlesversus the total number of particles in the ink. In yet anotherembodiment, at least about 75% or more of the particles (by weight or bynumber) are microflakes. The method includes coating a substrate withthe ink to form a precursor layer and processing the precursor layer ina suitable processing condition to form a film. The film may be used inthe formation of a semiconductor absorber for a photovoltaic device. Itshould be understood that suitable processing conditions may include,but are not limited to, atmosphere composition, pressure, and/ortemperature. In one embodiment, substantially all of the particles areflakes with a non-spherical, planar shape. In one embodiment, at least95% of all particles (based on weight of all particles combined) areflakes. In another embodiment, at least 99% of all particles (based onweight of all particles combined) are flakes. The flakes may becomprised of microflakes. In other embodiments, the flakes may becomprised of both microflakes and nanoflakes.

It should be understood that the planar shape of the microflakes mayprovide a number of advantages. As a nonlimiting example, the planarshape may create greater surface area contact between adjacentmicroflakes that allows the dense film to form at a lower temperatureand/or shorter time as compared to a film made from a precursor layerusing an ink of spherical nanoparticles wherein the nanoparticles have asubstantially similar material composition and the ink is otherwisesubstantially identical to the ink of the present invention. The planarshape of the microflakes may also create greater surface area contactbetween adjacent microflakes that allows the dense film to form at anannealing temperature at least about 50 degrees C. less as compared to afilm made from a precursor layer using an ink of spherical nanoparticlesthat is otherwise substantially identical to the ink of the presentinvention.

The planar shape of the microflakes may create greater surface areacontact between adjacent microflakes relative to adjacent sphericalnanoparticles and thus promotes increased atomic intermixing as comparedto a film made from a precursor layer made from an ink of the presentinvention. The planar shape of the microflakes creates a higher packingdensity in the dense film as compared to a film made from a precursorlayer made from an ink of spherical nanoparticles of the samecomposition that is otherwise substantially identical to the ink of thepresent invention.

The planar shape of the microflakes may also create a packing density ofat least about 70% in the precursor layer. The planar shape of themicroflakes may create a packing density of at least about 80% in theprecursor layer. The planar shape of the microflakes may create apacking density of at least about 90% in the precursor layer. The planarshape of the microflakes may create a packing density of at least about95% in the precursor layer. Packing density may be mass/volume,solids/volume, or non-voids/volume.

The planar shape of the microflakes results in grain sizes of at leastabout 1 micron in the semiconductor absorber of a photovoltaic device.The planar shape of the microflakes may results in grain sizes of atleast about 0.5 μm in at least one dimension in the semiconductorabsorber of a photovoltaic device. In other embodiments, the microflakesresults in grain sizes of at least about 0.1 μm in at least onedimension in the semiconductor absorber of a photovoltaic device. Instill further embodiments, the microflakes results in grain sizes of atleast about 0.1 μm in at least one dimension in the semiconductorabsorber of a photovoltaic device. The planar shape of the microflakesmay result in grain sizes of at least about 0.3 μm wide in thesemiconductor absorber of a photovoltaic device. In other embodiments,the planar shape of the microflakes results in grain sizes of at leastabout 0.3 μm wide in the semiconductor absorber of a photovoltaic devicewhen the microflakes are formed from one or more of the following:copper selenide, indium selenide, or gallium selenide.

The planar shape of the microflakes provides a material property toavoid rapid and/or preferential settling of the particles when formingthe precursor layer. The planar shape of the microflakes provides amaterial property to avoid rapid and/or preferential settling ofmicroflakes having different material compositions, when forming theprecursor layer. The planar shape of the microflakes provides a materialproperty to avoid rapid and/or preferential settling of microflakeshaving different particle sizes, when forming the precursor layer.

The planar shape of the microflakes provides a material property toavoid undesired grouping of microflakes of a particular class in the inkand thus enables an evenly dispersed solution of microflakes. The planarshape of the microflakes provides a material property to avoid undesiredgrouping of microflakes of a specific material composition in the inkand thus enables an evenly dispersed solution of microflakes. The planarshape of the microflakes provides a material property to avoid groupingof microflakes of a specific phase separation in the precursor layerresulting from the ink. The microflakes have a material property thatreduces surface tension at interface between microflakes in the ink anda carrier fluid to improve dispersion quality.

In one embodiment of the present invention, the ink may be formulated byuse of a low molecular weight dispersing agent whose inclusion iseffective due to favorable interaction of the dispersing agent with theplanar shape of the microflakes. The ink may be formulated by use of acarrier liquid and without a dispersing agent. The planar shape of themicroflakes provides a material property to allow for a more evendistribution of group IIIA material throughout in the dense film ascompared to a film made from a precursor layer made from an ink ofspherical nanoparticles that is otherwise substantially identical to theink of the present invention. In another embodiment, the microflakes maybe of random planar shape and/or a random size distribution.

The microflakes may be of non-random planar shape and/or a non-randomsize distribution. The microflakes may each have a length less thanabout 5 microns and greater than about 500 nm. The microflakes may eachhave a length between about 3 microns and about 500 nm. The particlesmay be microflakes having lengths of greater than about 500 nm. Theparticles may be microflakes having lengths of greater than about 750nm. The microflakes may each have a thickness of about 100 nm or less.The particles may be microflakes having thicknesses of about 75 nm orless. The particles may be microflakes having thicknesses of about 50 nmor less. The microflakes may each have a thickness less than about 20nm. The microflakes may have lengths of less than about 2 microns andthicknesses of less than about 100 nm. The microflakes may have lengthsof less than about 1 microns and a thicknesses of less than about 50 nm.The microflakes may have an aspect ratio of at least about 10 or more.The microflakes have an aspect ratio of at least about 15 or more.

Optionally, the microflakes may be oxygen-free. The microflakes may be asingle metal. The microflakes may be an alloy of group IB, IIIAelements. The microflakes may be a binary alloy of group IB, IIIAelements. The microflakes may be a ternary alloy of group IB, IIIAelements. The microflakes may be a quaternary alloy of group IB, IIIA,and/or VIA elements. The microflakes may be group IB-chalcogenideparticles and/or group IIIA-chalcogenide particles. Again, the particlesmay be particles that are substantially oxygen-free, which may includethose that include less than about 1 wt % of oxygen. Other embodimentsmay use materials with less than about 5 wt % of oxygen. Still otherembodiments may use materials with less than about 3 wt % oxygen. Stillother embodiments may use materials with less than about 2 wt % oxygen.Still other embodiments may use materials with less than about 0.5 wt %oxygen. Still other embodiments may use materials with less than about0.1 wt % oxygen.

Embodiments of the present invention may create particles withoutgrinding contamination instead of um-size (past), or wet-chemicalsynthesis (harder to make flakes and/or more expensive and/or use ofnasty solvents). Optionally, pin-hole free deposition of well-packedflakes may be achieved using embodiments of the present invention. Thisdue in part the tight packing of flakes and/or the ink created by theflake particles. Optionally, additional chalcogen at atmosphericpressure. Embodiments of the present invention may involve no additionalevaporation steps (of In, Ga, and Se), the process being all non-vacuum.Optionally, size reduction using the steps herein gives flakes andresults in more uniform composition from particle to particle, whereastheir wet chemical synthesis will result in more variation in Ga/IIIfrom particle to particle.

In one embodiment of the present invention, the coating step occurs atroom temperature. The coating step may occur at atmospheric pressure.The method may further comprise depositing a film of selenium onto thedense film. The processing step may be accelerated via thermalprocessing techniques using at least one of the following: pulsedthermal processing, exposure to a laser beam, or heating via IR lamps,and/or similar or related methods, or a muffle or furnace made frommetal, graphite, or ceramic. If a muffle is used in one embodiment, theheating elements are located outside the muffle. In this embodiment, themuffle itself may be a long rectangular or other cross-sectional shapedtube. The processing may comprise of heating the precursor layer to atemperature greater than about 375° C. but less than a meltingtemperature of the substrate for a period of less than 15 minutes. Theprocessing may comprise of heating the precursor layer to a temperaturegreater than about 375° C. but less than a melting temperature of thesubstrate for a period of 1 minute or less.

In another embodiment of the present invention, processing may becomprised of heating the precursor layer to an annealing temperature butless than a melting temperature of the substrate for a period of 1minute or less. The suitable atmosphere may be comprised of a hydrogenatmosphere. In another embodiment of the present invention, the suitableatmosphere comprises a nitrogen atmosphere. In yet another embodiment,the suitable atmosphere comprises a carbon monoxide atmosphere. Thesuitable atmosphere may be comprised of an atmosphere having less thanabout 10% hydrogen. The suitable atmosphere may be comprised of anatmosphere having 100% hydrogen. The suitable atmosphere may becomprised of an atmosphere containing selenium or a mixture of hydrogenand seleniu. The suitable atmosphere may be comprised of an atmosphereof a non-oxygen chalcogen. In one embodiment of the present invention,the suitable atmosphere may comprise of a selenium atmosphere providinga partial pressure greater than or equal to vapor pressure of seleniumin the precursor layer. In another embodiment, the suitable atmospheremay comprise of a non-oxygen atmosphere containing chalcogen vapor at apartial pressure of the chalcogen greater than or equal to a vaporpressure of the chalcogen at the processing temperature and processingpressure to minimize loss of chalcogen from the precursor layer, whereinthe processing pressure is a non-vacuum pressure. In yet anotherembodiment, the chalcogen atmosphere may be used with one or more binarychalcogenides (in any shape or form) at a partial pressure of thechalcogen greater than or equal to a vapor pressure of the chalcogen atthe processing temperature and processing pressure to minimize loss ofchalcogen from the precursor layer, wherein optionally, the processingpressure is a non-vacuum pressure. The suitable process may includemoving from one suitable atmosphere to another suitable atmosphere.

In yet another embodiment of the present invention, prior to the step offormulating the ink, there is included a step of creating microflakes.The creating step comprises of providing feedstock particles containingat least one element of groups IB, IIIA, and/or VIA, whereinsubstantially each of the feedstock particles have a composition ofsufficient malleability to form a planar shape from a non-planarstarting shape and milling the feedstock particles to reduce at leastthe thickness of each particle to less than 100 nm. The milling step mayoccur in an oxygen-free atmosphere to create substantially oxygen-freemicroflakes. In some embodiments of the present invention, microflakesmay have lengths of greater than about 500 nm. In some embodiments ofthe present invention, microflakes may have lengths of greater thanabout 750 nm. The microflakes may have thicknesses of at least about 75nm. The substrate may be a rigid substrate. The substrate may be aflexible substrate. The substrate may be an aluminum foil substrate,stainless steel substrate, titanium substrate, copper or a polymersubstrate, which is a flexible substrate in a roll-to-roll manner(either continuous or segmented) using a commercially available webcoating system. The rigid substrate may be comprised of at least onematerial selected from the group: glass, soda-lime glass, steel,stainless steel, aluminum, polymer, ceramic, metal plates, metallizedceramic plates, metallized polymer plates, metallized glass plates,and/or any single or multiple combinations of the aforementioned. Thesubstrate may be at different temperatures than the precursor layerduring processing. This may enable the substrate to use materials thatwould melt or become unstable at the processing temperature of theprecursor layer. Optionally, this may involve actively cooling thesubstrate during processing.

In yet another embodiment of the present invention, a method is providedfor formulating an ink of particles wherein a majority of the particlesare microflakes each containing at least one element from group IB, IIIAand/or VIA and having a non-spherical, planar shape, wherein the overallamounts of the elements from group IB, IIIA and/or VIA contained in theink are such that the ink has a desired stoichiometric ratio of theelements. The method may include coating a substrate with the ink toform a precursor layer, and processing the precursor layer to form adense film for growth of a semiconductor absorber of a photovoltaicdevice. In one embodiment, at least 60% of the particles (by weight orby number) are microflakes. In yet another embodiment, at least 70% ofthe particles (by weight or by number) are microflakes. In anotherembodiment, at least 80% of the particles (by weight or by number) aremicroflakes. In another embodiment, at least 90% of the particles (byweight or by number) are microflakes. In another embodiment, at least95% of the particles (by weight or by number) are microflakes.

In another embodiment, a liquid ink may be made using one or more liquidmetals. For example, an ink may be made starting with a liquid and/ormolten mixture of Gallium and/or Indium. Copper nanoparticles may thenbe added to the mixture, which may then be used as the ink/paste. Coppernanoparticles are available commercially. Alternatively, the temperatureof the Cu—Ga—In mixture may be adjusted (e.g. cooled) until a solidforms. The solid may be ground at that temperature until smallnanoparticles (e.g., less than 5 nm) are present. Selenium may be addedto the ink and/or a film formed from the ink by exposure to seleniumvapor, e.g., before, during, or after annealing.

In yet another embodiment of the present invention, a process isdescribed comprising of formulating a dispersion of solid and/or liquidparticles comprising group IB and/or IIIA elements, and, optionally, atleast one group VIA element. The process includes depositing thedispersion onto a substrate to form a layer on the substrate andreacting the layer in a suitable atmosphere to form a film. In thisprocess, at least one set of the particles are inter-metallic particlescontaining at least one group IB-IIIA inter-metallic phase. Any of theabove embodiments may use flakes (micro flakes or nanoflakes) thatcontain an inter-metallic phase as described herein.

In yet another embodiment of the present invention, a composition isprovided comprised of a plurality of particles comprising group IBand/or IIIA elements, and, optionally, at least one group VIA element.At least one set of the particles contains at least one group IB-IIIAinter-metallic alloy phase.

In a still further embodiment of the present invention, the method mayinclude formulating a dispersion of particles comprising group IB and/orIIIA elements, and, optionally, at least one group VIA element. Themethod may include depositing the dispersion onto a substrate to form alayer on the substrate and reacting the layer in a suitable atmosphereto form a film. At least one set of the particles contain a groupIB-poor, group IB-IIIA alloy phase. In some embodiments, group IB-poorparticles contribute less than about 50 molar percent of group IBelements found in all of the particles. The group IB-poor, group IB-IIIAalloy phase particles may be a sole source of one of the group IIIAelements. The group IB-poor, group IB-IIIA alloy phase particles maycontain an inter-metallic phase and may be a sole source of one of thegroup IIIA elements. The group IB-poor, group IB-IIIA alloy phaseparticles may contain an inter-metallic phase and are a sole source ofone of the group IIIA elements. The group IB-poor, group IB-IIIA alloyphase particles may be Cu₁In₂ particles and are a sole source of indiumin the material.

It should be understood that for any of the foregoing the film and/orfinal compound may include a group IB-IIIA-VIA compound. The reactingstep may comprise of heating the layer in the suitable atmosphere. Thedepositing step may include coating the substrate with the dispersion.At least one set of the particles in the dispersion may be in the formof nanoglobules. At least one set of the particles in the dispersion maybe in the form of nanoglobules and contain at least one group IIIAelement. At least one set of the particles in the dispersion may be inthe form of nanoglobules comprising of a group IIIA element in elementalform. In some embodiments of the present invention, the inter-metallicphase is not a terminal solid solution phase. In some embodiments of thepresent invention, the inter-metallic phase is not a solid solutionphase. The inter-metallic particles may contribute less than about 50molar percent of group IB elements found in all of the particles. Theinter-metallic particles may contribute less than about 50 molar percentof group IIIA elements found in all of the particles. The inter-metallicparticles may contribute less than about 50 molar percent of the groupIB elements and less than about 50 molar percent of the group IIIAelements in the dispersion deposited on the substrate. Theinter-metallic particles may contribute less than about 50 molar percentof the group IB elements and more than about 50 molar percent of thegroup IIIA elements in the dispersion deposited on the substrate. Theinter-metallic particles may contribute more than about 50 molar percentof the group IB elements and less than about 50 molar percent of thegroup IIIA elements in the dispersion deposited on the substrate. Themolar percent for any of the foregoing may be based on a total molarmass of the elements in all particles present in the dispersion. In someembodiments, at least some of the particles have a platelet shape. Insome embodiments, a majority of the particles have a platelet shape. Inother embodiments, substantially all of the particles have a plateletshape.

For any of the foregoing embodiments, an inter-metallic material for usewith the present invention is a binary material. The inter-metallicmaterial may be a ternary material. The inter-metallic material maycomprise of Cu₁In₂. The inter-metallic material may be comprised of acomposition in a δ phase of Cu₁In₂. The inter-metallic material may becomprised of a composition in between a δ phase of Cu₁In₂ and a phasedefined by Cu16In9. The inter-metallic material may be comprised ofCu₁Ga₂. The inter-metallic material may be comprised of an intermediatesolid-solution of Cu₁Ga₂. The inter-metallic material may be comprisedof Cu₆₈Ga₃₈. The inter-metallic material may be comprised of Cu₇₀Ga₃₀.The inter-metallic material may be comprised of Cu₇₅Ga₂₅. Theinter-metallic material may be comprised of a composition of Cu—Ga of aphase in between the terminal solid-solution and an intermediatesolid-solution next to it. The inter-metallic may be comprised of acomposition of Cu—Ga in a γ1 phase (about 31.8 to about 39.8 wt % Ga).The inter-metallic may be comprised of a composition of Cu—Ga in a γ2phase (about 36.0 to about 39.9 wt % Ga). The inter-metallic may becomprised of a composition of Cu—Ga in a γ3 phase (about 39.7 to about−44.9 wt % Ga). The inter-metallic may be comprised of a composition ofCu—Ga in a phase between γ2 and γ3. The inter-metallic may be comprisedof a composition of Cu—Ga in a phase between the terminal solid solutionand γ1. The inter-metallic may be comprised of a composition of Cu—Ga ina 0 phase (about 66.7 to about 68.7 wt % Ga). The inter-metallicmaterial may be comprised of Cu-rich Cu—Ga. Gallium may be incorporatedas a group IIIA element in the form of a suspension of nanoglobules.Nanoglobules of gallium may be formed by creating an emulsion of liquidgallium in a solution. Gallium nanoglobules may be created by beingquenched below room temperature.

A process according to the any of the foregoing embodiments of thepresent invention may include maintaining or enhancing a dispersion ofliquid gallium in solution by stirring, mechanical means,electromagnetic means, ultrasonic means, and/or the addition ofdispersants and/or emulsifiers. The process may include adding a mixtureof one or more elemental particles selected from: aluminum, tellurium,or sulfur. The suitable atmosphere may contain selenium, sulfur,tellurium, H₂, CO, H₂Se, H₂S, Ar, N₂ or combinations or mixture thereof.The suitable atmosphere may contain at least one of the following: H₂,CO, Ar, and N₂. One or more classes of the particles may be doped withone or more inorganic materials. Optionally, one or more classes of theparticles are doped with one or more inorganic materials chosen from thegroup of aluminum (Al), sulfur (S), sodium (Na), potassium (K), orlithium (Li).

Optionally, embodiments of the present invention may include having acopper source that does not immediately alloy with In, and/or Ga. Oneoption would be to use (slightly) oxidized copper. The other optionwould be to use CuxSey. Note that for the (slightly) oxidized copperapproach, a reducing step may be desired. Basically, if elemental copperis used in liquid In and/or Ga, speed of the process between inkpreparation and coating should be sufficient so that the particles havenot grown to a size that will result in thickness non-uniform coatings.

It should be understood that the temperature range may that of thesubstrate only since that is typically the only one that should not beheated above its melting point. This holds for the lowest meltingmaterial in the substrate, being Al and other suitable substrates.

In yet another embodiment of the present invention, a material isprovided that comprises of a plurality of microflakes having a materialcomposition containing at least one element from Groups IB, IIIA, and/orVIA. The microflakes may be created by milling precursor particlescharacterized by a precursor composition that provides sufficientmalleability to form a planar shape from a non-planar starting shapewhen milled, and wherein overall amounts of elements from Groups IB,IIIA and/or VIA contained in the precursor particles combined are at adesired stoichiometric ratio of the elements. It should also beunderstood that other flakes such as but not limited to nanoflakes mayalso be used to form the precursor material.

In one embodiment of the present invention, the milling transforms atleast about 50% of the precursor particles into microflakes. In otherembodiments, milling transforms at least about 95% of the precursorparticles into microflakes. This may be by percent weight of all of theparticles or based only on the number of particles. Optionally, themilling transforms substantially all of the precursor particles intomicroflakes. The precursor particles may be about 10 microns or largerwhen measured along their longest dimension. The milling may occur in anoxygen free atmosphere to create oxygen free microflakes. The millingmay occur in an inert gas environment to create oxygen free microflakes.The milling may occur at room temperature. The milling may occur at acryogenic temperature. The milling may occur at a milling temperaturewherein all elements in the precursor particles are solids and have theprecursor particles have a sufficient ductility at the millingtemperature to form the planar shape from the non-planar starting shape.The milling may occur at a temperature less than about 15 degrees C. Themilling may occur at a temperature less than about −200 degrees C.

Optionally, the precursor particles may be single metal particles. Theprecursor particles may be elemental particles. The precursor particlesmay be alloy particles. The precursor particles may be binary alloyparticles. The precursor particles may be ternary alloy particles. Theprecursor particles may be quaternary alloy particles. The precursorparticles may be solid solution particles. The microflakes may becomprised of only Group IIIA materials. The microflakes may be comprisedof only Group IB and Group IIIA materials. The microflakes may becomprised of only Group IB and Group VIA materials. The microflakes maybe comprised of only Group IIIA and Group VIA materials. The molar ratioof Group IB material to Group IIIA material in the plurality ofmicroflakes may be larger than about 1.0. The precursor particles may beelemental particles and wherein milling forms alloy microflakes from theelemental particles. The precursor particles may be chalcogenideparticles characterized by a stoichiometric ratio of elements thatprovides the precursor particles with sufficient ductility to form aplanar shape from a non-planar starting shape. The precursor particlesmay be selected from one of the following: copper selenide, indiumselenide, or gallium selenide. The stoichiometric ratio of elements mayvary between microflakes so long as the overall amount in all of themicroflakes combined is at the desired stoichiometric ratio. Thematerial may have been size discriminated such that the microflakes toexclude microflakes above a desired length. The microflakes may excludemicroflakes above a desired thickness. The size variation may becontrolled such that the microflakes deviate less than about 30% fromthe mean length and about 30% from mean thickness. The particle sizedistribution may be such that one standard deviation from a mean lengthof the microflakes is less than 100 nm. The particle size distributionmay be such that one standard deviation from a mean length of themicroflakes is less than 50 nm. The particle size distribution may besuch that one standard deviation from a mean thickness of themicroflakes is less than 10 nm. The particle size distribution may besuch that one standard deviation from a mean thickness of themicroflakes is less than 5 nm. The particle size distribution may besuch that substantially each of the microflakes has a thickness about100 nm or less. The particle size distribution may be such thatmicroflakes are substantially void free particles.

Optionally, the microflakes may have a coating with at least one layerof material containing a group VIA element. The microflakes may have acoating the microflakes with at least one layer of material containingselenium and/or a selenide. The microflakes may form a dry powder. Themicroflakes may have an aspect ratio of at least about 10 or more. Themicroflakes may have an aspect ratio of at least about 15 or more.

In a still further embodiment of the present invention, a solar cell isprovided that comprises of a substrate, a back electrode formed over thesubstrate, a p-type semiconductor thin film formed over the backelectrode, an n-type semiconductor thin film formed so as to constitutea pn junction with the p-type semiconductor thin film, and a transparentelectrode formed over the n-type semiconductor thin film. The p-typesemiconductor thin film results by processing a dense film formed from aplurality of microflakes having a material composition containing atleast one element from Groups IB, IIIA, and/or VIA, wherein the densefilm has a void volume of about 26% or less. The dense film may be asubstantially void free film.

Optionally, the molar ratio of Group IB material to Group IIIA materialin the plurality of microflakes is larger than 1.0. The microflakes maybe substantially oxygen free microflakes. The microflakes may be singlemetal particles. The microflakes may be elemental particles. Themicroflakes may be alloy particles. The microflakes may be binary alloyparticles. The microflakes may be ternary alloy particles. Themicroflakes may be quaternary alloy particles. The microflakes may besolid solution particles. The microflakes may comprise of only GroupIIIA materials. The microflakes may comprise of only Group IB and GroupIIIA materials. The microflakes may comprise of only Group IB and GroupVIA materials. The microflakes may comprise of only Group IIIA and GroupVIA materials. The microflakes may be selected from one of thefollowing: copper selenide, indium selenide, or gallium selenide. Themicroflakes may have a size distribution such that one standarddeviation from a mean length of the microflakes is less than 100 nm. Themicroflakes may have a size distribution such that one standarddeviation from a mean length of the microflakes is less than 50 nm. Themicroflakes may have a size distribution such that one standarddeviation from a mean thickness of the microflakes is less than 10 nm.The microflakes may have a size distribution such that one standarddeviation from a mean thickness of the microflakes is less than 5 nm.The microflakes may have a composition such that the stoichiometricratio of elements varies between microflakes so long as the overallamount in all of the particles combined is at the desired stoichiometricratio. The microflakes may have an aspect ratio of at least about 10 ormore. The microflakes may have an aspect ratio of at least about 15 ormore. The microflakes may have a random planar shape and/or a randomsize distribution. The microflakes may be of non-random planar shapeand/or a non-random size distribution. The microflakes may each have athickness less than about 100 nm. The microflakes may each have athickness less than about 20 nm. The microflakes may each have a lengthand/or largest lateral dimension of less than about 2 microns and athickness of less than 100 nm. The microflakes may have a length of lessthan about 1 microns and a thickness of less than 50 nm.

Optionally, the film may be formed by heating a precursor layer ofmicroflakes to a temperature greater than about 375° C. but less than amelting temperature of the substrate for a period of 1 minute or less.The dense film may be formed by heating a precursor layer of microflakesto an annealing temperature but less than a melting temperature of thesubstrate for a period of 1 minute or less. Dense film formation may beaccelerated via thermal processing techniques using at least one of thefollowing: pulsed thermal processing, laser beams, or heating via IRlamps. The substrate may be a flexible substrate. The substrate may be arigid substrate.

A further understanding of the nature and advantages of the inventionwill become apparent by reference to the remaining portions of thespecification and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1D are schematic cross-sectional diagrams illustratingfabrication of a film according to an embodiment of the presentinvention.

FIGS. 2A and 2B are magnified side view and magnified top-down view ofmicroflakes according to one embodiment of the present invention.

FIG. 2C is a magnified top-down view of a nanoflake according to oneembodiment of the present invention.

FIG. 3 shows a schematic of a milling system according to the oneembodiment of the present invention.

FIG. 4 shows a schematic of a roll-to-roll manufacturing systemaccording to the one embodiment of the present invention.

FIG. 5 shows a cross-sectional view of a photovoltaic device accordingto one embodiment of the present invention.

FIG. 6 shows a flowchart of a method according to one embodiment of thepresent invention.

FIG. 7 shows a module having a plurality of photovoltaic devicesaccording to one embodiment of the present invention.

FIGS. 8A-8C show a schematic view of planar particles used withspherical particles according to one embodiment of the presentinvention.

FIGS. 9A-9D show a schematic view of a discrete printed layer of achalcogen source used with planar particles according to one embodimentof the present invention.

FIG. 9E shows particles having a shell of chalcogen according to oneembodiment of the present invention.

FIGS. 10A-10C show the use of chalcogenide planar particles according toone embodiment of the present invention.

FIGS. 11A-11C show a nucleation layer according to one embodiment of thepresent invention.

FIGS. 12A-12B show schematics of devices which may be used to create anucleation layer through a thermal gradient.

FIGS. 13A-13F show the use of a chemical gradient according to oneembodiment of the present invention.

FIG. 14 shows a roll-to-roll system according to the present invention.

FIGS. 15A-15D show a schematic of a system using a chalcogen materialaccording to one embodiment of the present invention.

FIG. 15E shows a schematic of a system using a chalcogen vaporenvironment according to one embodiment of the present invention.

FIG. 15F shows a schematic of a system using a chalcogen vaporenvironment according to one embodiment of the present invention.

FIG. 15G shows a schematic of a system using a chalcogen vaporenvironment according to one embodiment of the present invention.

FIG. 16A shows one embodiment of a system for use with rigid substratesaccording to one embodiment of the present invention.

FIG. 16B shows one embodiment of a system for use with rigid substratesaccording to one embodiment of the present invention.

FIGS. 17-19 show the use of inter-metallic material to form a filmaccording to embodiments of the present invention.

FIG. 20 is a cross-sectional view showing the use of multiple layers toform a film according to embodiments of the present invention.

FIG. 21 shows feedstock material being processed according toembodiments of the present invention.

FIGS. 22A and 22B show features of flakes according to embodiments ofthe present invention.

FIGS. 23A and 23B show features of platelets.

FIGS. 24A-24E show coating stabilization of particles according to oneor more embodiments of the present invention.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention, as claimed. It may be notedthat, as used in the specification and the appended claims, the singularforms “a”, “an” and “the” include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a material”may include mixtures of materials, reference to “a compound” may includemultiple compounds, and the like. References cited herein are herebyincorporated by reference in their entirety, except to the extent thatthey conflict with teachings explicitly set forth in this specification.

In this specification and in the claims which follow, reference will bemade to a number of terms which shall be defined to have the followingmeanings:

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, if a device optionally contains a feature for a barrierfilm, this means that the barrier film feature may or may not bepresent, and, thus, the description includes both structures wherein adevice possesses the barrier film feature and structures wherein thebarrier film feature is not present.

According to embodiments of the present invention, an active layer for aphotovoltaic device may be fabricated by first formulating an ink ofnon-spherical particles each containing at least one element from groupsIB, IIIA and/or VIA, coating a substrate with the ink to form aprecursor layer, and heating the precursor layer to form a dense film.Optionally, it should be understood that in some embodiments,densification of the precursor layer may not be needed, particularly ifthe precursor materials are oxygen-free or substantially oxygen free.Thus, the heating step may optionally be skipped if the particles areprocessed air-free and are oxygen-free. In a preferred embodiment, thenon-spherical particles are microflakes that are substantially planar inshape. The dense film may be processed in a suitable atmosphere to forma group IB-IIIA-VIA compound. In other embodiments, the precursor layerforms a layer with a group IB-IIIA-VIA compound in a one step process.Optionally, others may take one or more steps. The resulting groupIB-IIIA-VIA compound is preferably a compound of Cu, In, Ga and selenium(Se) or sulfur S of the form CuIn_((1-x))Ga_(x)S_(2(1-y))Se_(2y), where0≦x≦1 and 0≦y≦1. It should be understood that reduction and/ordensification of the precursor layer may not be needed in someembodiments, particularly if the precursor materials are oxygen-free orsubstantially oxygen free. Thus, the heating step may optionally beskipped if the particles are processed air-free and are oxygen-free.Thus in such an embodiment, instead of using an annealing step todensify the precursor and remove oxygen, the process may skip straightto the reactive heating step in which the precursor material is reactedtypically in the presence of a group VIA material to form the finalgroup IB-IIIA-VIA material. It should be understood that someembodiments grow an absorber or compound containing both Se and S.Optionally, it should Some embodiments may also form the desiredsemiconductor film in a one step process

It should be understood that group IB, IIIA, and VIA elements other thanCu, In, Ga, Se, and S may be included in the description of theIB-IIIA-VIA materials described herein, and that the use of a hyphen(“-”e.g., in Cu—Se or Cu—In—Se) does not indicate a compound, but ratherindicates a coexisting mixture of the elements joined by the hyphen. Itis also understood that group IB is sometimes referred to as group 11,group IIIA is sometimes referred to as group 13 and group VIA issometimes referred to as group 16. Furthermore, elements of group VIA(16) are sometimes referred to as chalcogens. Where several elements canbe combined with or substituted for each other, such as In and Ga, orSe, and S, in embodiments of the present invention, it is not uncommonin this art to include in a set of parentheses those elements that canbe combined or interchanged, such as (In, Ga) or (Se, S). Thedescriptions in this specification sometimes use this convenience.Finally, also for convenience, the elements are discussed with theircommonly accepted chemical symbols. Group IB elements suitable for usein the method of this invention include copper (Cu), silver (Ag), andgold (Au). Preferably the group IB element is copper (Cu). Group IIIAelements suitable for use in the method of this invention includegallium (Ga), indium (In), aluminum (Al), and thallium (Tl). Preferablythe group IIIA element is gallium (Ga) or indium (In). Group VIAelements of interest include selenium (Se), sulfur (S), and tellurium(Te), and preferably the group VIA element is either Se and/or S. Itshould be understood that mixtures such as, but not limited to, alloys,solid solutions, and compounds of any of the above can also be used.

Method of Forming a Film

Referring now to FIG. 1, one method of forming a semiconductor filmaccording to the present invention will now be described. It should beunderstood that the present embodiment of the invention uses non-vacuumtechniques to form the semiconductor film. Other embodiments, however,may form the film under a vacuum environment, and the present inventionusing non-spherical particles is not limited to only non-vacuum coatingtechniques.

As seen in FIG. 1A, a substrate 102 is provided on which the precursorlayer 106 (see FIG. 1B) will be formed. By way of non-limiting example,the substrate 102 may be made of a metal such as aluminum. In otherembodiments, metals such as, but not limited to, stainless steel,molybdenum, titanium, copper, metallized plastic films, coated metalfoils, or combinations of the foregoing may be used as the substrate102. Alternative substrates include but are not limited to ceramics,glasses, and the like. Any of these substrates may be in the form offoils, sheets, rolls, or the like, or combinations thereof. Depending onthe material of the substrate 102, it may be useful to coat a surface ofthe substrate 102 with a contact layer 104 to promote electrical contactbetween the substrate 102 and the absorber layer that is to be formed onit, and/or to limit reactivity of the substrate 102 in subsequent steps,and/or to promote higher quality absorber growth. As a non-limitingexample, when the substrate 102 is made of aluminum, the contact layer104 may be but is not limited to a layer of molybdenum. For the purposesof the present discussion, the contact layer 104 may be regarded asbeing part of the substrate. As such, any discussion of forming ordisposing a material or layer of material on the substrate 102 includesdisposing or forming such material or layer on the contact layer 104, ifone is used. Optionally, other layers of materials may also be used withthe contact layer 104 for insulation or other purposes and stillconsidered part of the substrate 102. It should be understood that thecontact layer 104 may comprise of more than one type or more than onediscrete layer of material. Optionally, some embodiments may use any oneand/or combinations of the following for the contact layer: a copper,aluminum, chromium, molybdenum, vanadium, etc. and/or iron-cobaltalloys. Optionally, a diffusion barrier layer 103 (shown in phantom) maybe included and layer 103 may be electrically conductive or electricallynon-conductive. As non-limiting examples, the layer 103 may be composedof any of a variety of materials, including but not limited to chromium,vanadium, tungsten, or compounds such as nitrides (including tantalumnitride, tungsten nitride, titanium nitride, silicon nitride, zirconiumnitride, and/or hafnium nitride), oxides (including Al2O3 or SiO2),carbides (including SiC), and/or any single or multiple combination ofthe foregoing. Optionally, a diffusion barrier layer 105 (shown inphantom) may be on the underside of substrate 102 and be comprised of amaterial such as but not limited to chromium, vanadium, tungsten, orcompounds such as nitrides (including tantalum nitride, tungstennitride, titanium nitride, silicon nitride, zirconium nitride, and/orhafnium nitride), oxides (including Al2O3 or SiO2), carbides (includingSiC), and/or any single or multiple combination of the foregoing. Thelayers 103 and/or 105 may be adapted for use with any of the embodimentsdescribed herein.

Referring now to FIG. 1B, a precursor layer 106 is formed over thesubstrate 102 by coating the substrate 102 with a dispersion such as butnot limited to an ink. As one non-limiting example, the ink may becomprised of a carrier liquid mixed with particles such as but notlimited to microflakes 108 and has a rheology that allows the ink to besolution-deposited over the substrate 102. In one embodiment, thepresent invention may use a single dry powder or a mixture of two ormore dry powders mixed with the vehicle containing or not containing adispersant, and sonicated before coating. Optionally, the inks may bealready formulated as the precursor materials are formed in a horizontalbead mill. In the case of mixing a plurality of flake compositions, theproduct may be mixed from various suspensions. This mixing could be bysonication but other forms of mechanical agitation and/or another millmay also be used. The ink used to form the precursor layer 106 maycontain non-spherical particles 108 such as but not limited tomicroflakes and/or nanoflakes. It should also be understood that the inkmay optionally use both non-spherical and spherical particles in any ofa variety of relative proportions.

FIG. 1B includes a close-up view of the particles in the precursor layer106, as seen in the enlarged image. Although not limited to thefollowing, the particles may be microflakes 108 that have non-sphericalshapes and are substantially planar on at least one side. A moredetailed view of one embodiment of the microflakes 108 can be found inFIGS. 2A and 2B of U.S. patent application Ser. No. 11/362,266 filedFeb. 23, 2006 and fully incorporated herein by reference. Microflakesmay be defined as particles having at least one substantially planarsurface with a length and/or largest lateral dimension of about 500 nmor more and the particles have an aspect ratio of about 2 or more. Inother embodiments, the microflake is a substantially planar structurewith thickness of between about 10 and about 250 nm and lengths betweenabout 500 nm and about 5 microns. It should be understood that in otherembodiments of the invention, microflakes may have lengths as large as10 microns. Although not limited to the following, at least some of thesolid group IIIA-particles may be processed into planar particles andadapted for use during solution deposition.

It should be understood that different types of microflakes 108 may beused to form the precursor layer 106. In one nonlimiting example, themicroflakes are elemental microflakes, i.e., microflakes having only asingle atomic species. The microflakes may be single metal particles ofCu, Ga, In, or Se. Some inks may have only one type of microflake. Otherinks may have two or more types of microflakes which may differ inmaterial composition and/or other quality such as but not limited toshape, size, interior architecture (e.g. a central core surrounded byone or more shell layers) exterior coating, or the like. In oneembodiment, the ink used for precursor layer 106 may contain microflakescomprising one or more group IB elements and microflakes comprising oneor more different group IIIA elements. Preferably, the precursor layer(106) contains copper, indium and gallium. In another embodiment, theprecursor layer 106 may be an oxygen-free layer containing copper,indium and gallium. Optionally, the ratio of elements in the precursorlayer may be such that the layer, when processed, forms a compound ofCuIn_(x)Ga_(1-x), where 0≦x≦1. Those of skill in the art will recognizethat other group IB elements may be substituted for Cu and other groupIIIA elements may be substituted for In and Ga. Optionally, theprecursor may contain Se as well, such as but not limited to Cu—In—Ga—Seplates. This is feasible if the precursor is oxygen-free anddensification is not needed. In still further embodiments, the precursormaterial may contain microflakes of group IB, IIIA, and VIA elements. Inone nonlimiting example, the precursor may contain Cu—In—Ga—Semicroflakes, which would be particularly advantageous if the microflakesare formed air free and densification prior to film formation is notneeded.

Optionally, the microflakes 108 in the ink may be alloy microflakes. Inone nonlimiting example, the microflakes may be binary alloy microflakessuch as but not limited to Cu—In, In—Ga, or Cu—Ga. Alternatively, themicroflakes may be a binary alloy of group IB, IIIA elements, a binaryalloy of Group IB, VIA elements, and/or a binary alloy of group IIIA,VIA elements. In other embodiments, the particles may be a ternary alloyof group IB, IIIA, and/or VIA elements. For example, the particles maybe ternary alloy particles of any of the above elements such as but notlimited to Cu—In—Ga. In other embodiments, the ink may contain particlesthat are a quaternary alloy of group IB, IIIA, and/or VIA elements. Someembodiments may have quaternary or multi-nary microflakes. The ink mayalso combine microflakes of different classes such as but not limited toelemental microflakes with alloy microflakes or the like. In onenonlimiting example, Cu—Ga microflakes may be used in combination withIn particles or flakes. Optionally, Cu—In microflakes may be used incombination with Ga particles or flakes. Optionally, In—Ga microflakesmay be used in combination with Cu particles or flakes. Optionally,Cu—In microflakes may be used in combination with Cu particles orflakes. Optionally, Cu—Ga microflakes may be used in combination with Cuparticles or flakes.

In one embodiment of the present invention, the microflakes used to formthe precursor layer 106 contains no oxygen other than those amountsunavoidably present as impurities. Optionally, the microflakes containless than about 0.1 wt % of oxygen. In other embodiments, themicroflakes contain less than about 0.5 wt % of oxygen. In still furtherembodiments, the microflakes contain less than about 1.0 wt % of oxygen.In yet another embodiment, the microflakes contain less than about 3.0wt % of oxygen. In other embodiments, the microflakes contain less thanabout 5.0 wt % of oxygen. Some embodiments may have a shell layer thatcontains 0 to 5 wt % of oxygen. Optionally, the shell may have about5-25 wt % of oxygen. Optionally, the shell may be a full oxide. Any ofthe foregoing may optionally be applied to any particles used with thepresent invention, regardless of shape or size. It should also beunderstood that the source of group VIA material may be added asdiscussed in commonly assigned, co-pending U.S. patent application Ser.No. 11/243,522 filed on Feb. 23, 2006 and fully incorporated herein byreference.

Optionally, the microflakes 108 in the ink may be chalcogenideparticles, such as but not limited to, a group IB or group IIIAselenide. In one nonlimiting example, the microflakes may be a groupIB-chalcogenide formed with one or more elements of group IB (new-style:group 11), e.g., copper (Cu), silver (Ag), and gold (Au). Examplesinclude, but are not limited to, Cu_(x)Se_(y), wherein x is in the rangeof about 1 to 10 and y is in the range of about 1 to 10. In someembodiments of the present invention, x<y. Alternatively, someembodiments may have selenides that are more selenium rich, such as butnot limited to, Cu₁Se_(x) (where x>1). This may provide an increasedsource of selenium as discussed in commonly assigned, co-pending U.S.patent application Ser. No. 11/243,522 filed on Feb. 23, 2006 and fullyincorporated herein by reference. Alternatively, some embodiments mayhave selenides that are selenium poor, such as but not limited to,Cu₁Se_(x) (where x<1) In another nonlimiting example, the microflakesmay be a group IIIA-chalcogenide formed with one or more elements ofgroup IIIA (new style: group 16), e.g., aluminum (Al), indium (In),gallium (Ga), and thallium (Tl). Examples include In_(x)Se_(y) andGa_(x)Se_(y) wherein x is in the range of about 1 to about 10 and y isin the range of about 1 to about 10. Still further, the microflakes maybe a Group IB-IIIA-chalcogenide compound of one or more group IBelements, one or more group IIIA elements and one or more chalcogens.Examples include CuInGa—Se₂. Other embodiments may replace the selenidecomponent with another group VIA element such as but not limited tosulfur, or combinations of multiple group VIA elements such as bothsulfur and selenium. Any of the foregoing may optionally apply to anyparticles used with the present invention, regardless of shape or size.

It should be understood that the ink used in the present invention mayinclude more than one type of chalcogenide microflakes. For example,some may include microflakes from both group IB-chalcogenide(s) andgroup IIIA-chalcogenide(s). Others may include microflakes fromdifferent group IB-chalcogenides with different stoichiometric ratios.Others may include microflakes from different group IIIA-chalcogenideswith different stoichiometric ratios.

Optionally, the microflakes 108 in the ink may also be particles of atleast one solid solution. In one nonlimiting example, the nano-powdermay contain copper-gallium solid solution particles, and at least one ofindium particles, indium-gallium solid-solution particles, copper-indiumsolid solution particles, and copper particles. Alternatively, thenano-powder may contain copper particles and indium-galliumsolid-solution particles.

One of the advantages of using microflake-based dispersions is that itis possible to vary the concentration of the elements within theprecursor layer 106 from top to bottom by building the precursor layerin a sequence of thinner sub-layers, which when combined, form theprecursor layer. The material may be deposited to form the first, secondlayer or subsequent sub-layers, and reacted in at least one suitableatmosphere to form the corresponding component of the active layer. Inother embodiment, the sub-layers may be reacted as the sub-layers aredeposited. The relative elemental concentration of the microflakes thatmake up the ink for each sub-layer may be varied. Thus, for example, theconcentration of gallium within the absorber layer may be varied as afunction of depth within the absorber layer. The precursor layer 106 (orselected constituent sub-layers, if any) may be deposited using aprecursor material formulated with a controlled overall compositionhaving a desired stoichiometric ratio. More details on one method ofbuilding a layer in a sequence of sub-layers can be found in commonlyassigned, copending U.S. patent application Ser. No. 11/243,492 filedOct. 3, 2005 and fully incorporated herein by reference for allpurposes.

It should be understood that the film may be a layer made from adispersion, such as but not limited to an ink, paste, or paint. A layerof the dispersion can be spread onto the substrate and annealed to formthe precursor layer 106. By way of example the dispersion can be made byforming oxygen-free microflakes containing elements from group IB, groupIIIA and intermixing these microflakes and adding them to a vehicle,which may encompass a carrier liquid (such as but not limited to asolvent), and any additives.

Generally, an ink may be formed by dispersing any of the aforementionedparticles (and/or other particles) in a vehicle containing a dispersant(e.g., a surfactant or polymer) along with (optionally) some combinationof other components commonly used in making inks. In some embodiments ofthe present invention, the ink is formulated without a dispersant orother additives. The carrier liquid may be an aqueous (water-based) ornon-aqueous (organic) solvent. Other components include, withoutlimitation, dispersing agents, binders, emulsifiers, anti-foamingagents, dryers, solvents, fillers, extenders, thickening agents, filmconditioners, anti-oxidants, flow and leveling agents, plasticizers andpreservatives, and oxidation inhibitors including reducing agents. Thesecomponents can be added in various combinations to improve the filmquality and optimize the coating properties of the microflakedispersion. An alternative method to mixing microflakes and subsequentlypreparing a dispersion from these mixed microflakes would be to prepareseparate dispersions for each individual type of microflake andsubsequently mixing these dispersions. It should be understood that, dueto favorable interaction of the planar shape of the microflakes with thecarrier liquid, some embodiments of the ink may be formulated by use ofa carrier liquid and without a dispersing agent.

The precursor layer 106 from the dispersion may be formed on thesubstrate 102 by any of a variety of solution-based coating techniquesincluding but not limited to wet coating, spray coating, spin coating,doctor blade coating, contact printing, top feed reverse printing,bottom feed reverse printing, nozzle feed reverse printing, gravureprinting, microgravure printing, reverse microgravure printing, commadirect printing, roller coating, slot die coating, curtain coatingmeyerbar coating, lip direct coating, dual lip direct coating, capillarycoating, ink-jet printing, jet deposition, spray deposition, and thelike, as well as combinations of the above and/or related technologies.The foregoing may apply to any embodiments herein, regardless ofparticle size or shape.

In some embodiments, extra chalcogen, alloys particles, or elementalparticles, e.g., micron- or sub-micron-sized chalcogen powder may bemixed into the dispersion containing the microflakes so that themicroflakes and extra chalcogen are deposited at the same time.Alternatively the chalcogen powder may be deposited on the substrate ina separate solution-based coating step before or after depositing thedispersion containing the microflakes. In other embodiment, group IIIAelemental material such as but not limited to gallium droplets may bemixed with the flakes. This is more fully described in commonlyassigned, copending U.S. patent application Ser. No. 11/243,522 filed onFeb. 23, 2006 and fully incorporated herein by reference. This maycreate an additional layer 107 (shown in phantom in FIG. 1C).Optionally, additional chalcogen may be added by any combination of (1)any chalcogen source that can be solution-deposited, e.g. a Se, S, orchalcogen-containing alloy nano- or micron-sized powder mixed into theprecursor layers or deposited as a separate layer, (2) chalcogen (e.g.,Se or S) evaporation, (3) an H₂Se (H₂S) atmosphere, (4) a chalcogen(e.g., Se or S) atmosphere, (5) an H₂ atmosphere, (6) an organo-seleniumatmosphere, e.g. diethylselenide or another organo-metallic material,(7) another reducing atmosphere, e.g. CO, and a (8) a wet chemicalreduction step, and a (9) heat treatment. The stoichiometric ratio ofmicroflakes to extra chalcogen, given as Se/(Cu+In+Ga+Se) may be in therange of about 0 to about 1000. This is purely exemplary andnonlimiting. Any of the foregoing may optionally apply to any particlesused with the present invention, regardless of shape or size.

Note that the solution-based deposition of the proposed mixtures ofmicroflakes does not necessarily have to be performed by depositingthese mixtures in a single step. In some embodiments of the presentinvention, the coating step may be performed by sequentially depositingmicroflake dispersions having different compositions of IB-, IIIA- andchalcogen-based particulates in two or more steps. For example, themethod may be to first deposit a dispersion containing an indiumselenide microflake (e.g. with an In-to-Se ratio of ˜1), andsubsequently deposit a dispersion of a copper selenide microflake (e.g.with a Cu-to-Se ratio of ˜1) and a gallium selenide microflake (e.g.with a Ga-to-Se ratio of ˜1) followed optionally by depositing adispersion of Se. This would result in a stack of three solution-baseddeposited layers, which may be heated together. Alternatively, eachlayer may be heated or sintered before depositing the next layer. Anumber of different sequences are possible. For example, a layer ofIn_(x)Ga_(y)Se_(z) with x≧0 (larger than or equal to zero), y≧0 (largerthan or equal to zero), and z≧0 (larger than or equal to zero), may beformed as described above on top of a uniform, dense layer ofCu_(w)In_(x)Ga_(y) with w≧0 (larger than or equal to zero), x≧0 (largerthan or equal to zero), and y≧0 (larger than or equal to zero), andsubsequently converting (heating) the two layers into CIGS.Alternatively a layer of Cu_(w)In_(x)Ga_(y) may be formed on top of auniform, dense layer of In_(x)Ga_(y)Se, and subsequently converting(heating) the two layers into CIGS.

In alternative embodiments, microflake-based dispersions as describedabove may further include elemental IB, and/or IIIA nanoparticles (e.g.,in metallic form). These nanoparticles may be in flake form, oroptionally, take other shapes such as but not limited to spherical,spheroidal, oblong, cubic, or other non-planar shapes. These particlesmay also include but is not limited to emulsions, molten materials,mixtures, and the like, in addition to solids. For exampleCu_(x)In_(y)Ga_(z)Se_(u) materials, with u>0 (larger than zero), withx≧0 (larger than or equal to zero), y≧0 (larger than or equal to zero),and z≧0 (larger than or equal to zero), may be combined with anadditional source of selenium (or other chalcogen) and metallic galliuminto a dispersion that is formed into a film on the substrate byheating. Metallic gallium nanoparticles and/or nanoglobules and/ornanodroplets may be formed, e.g., by initially creating an emulsion ofliquid gallium in a solution. Gallium metal or gallium metal in asolvent with or without emulsifier may be heated to liquefy the metal,which is then sonicated and/or otherwise mechanically agitated in thepresence of a solvent. Agitation may be carried out either mechanically,electromagnetically, or acoustically in the presence of a solvent withor without a surfactant, dispersant, and/or emulsifier. The galliumnanoglobules and/or nanodroplets can then be manipulated in the form ofa solid-particulate, by quenching in an environment either at or belowroom temperature to convert the liquid gallium nanoglobules into solidgallium nanoparticles. This technique is described in detail incommonly-assigned U.S. patent application Ser. No. 11/081,163 to MatthewR. Robinson and Martin R. Roscheisen entitled “Metallic Dispersion”, theentire disclosures of which are incorporated herein by reference.

Note that the method may be optimized by using, prior to, during, orafter the solution deposition and/or heating of one or more of theprecursor layers, any combination of (1) any chalcogen source that canbe solution-deposited, e.g. a Se or S nanopowder mixed into theprecursor layers or deposited as a separate layer, (2) chalcogen (e.g.,Se or S) evaporation, (3) an H₂Se (H₂S) atmosphere, (4) a chalcogen(e.g., Se or S) atmosphere, (5), an organo-selenium containingatmosphere, e.g. diethylselenide (6) an H₂ atmosphere, (7) anotherreducing atmosphere, e.g. CO, (8) a wet chemical reduction step, and a(9) heat treatment.

Referring now to FIG. 1C, the precursor layer 106 may then be processedin a suitable atmosphere to form a film. The film may be a dense film.In one embodiment, this involves heating the precursor layer 106 to atemperature sufficient to convert the ink (as-deposited ink. Note thatsolvent and possibly dispersant have been removed by drying) to afilm.). The temperature may be between about 375° C. and about 525° C.(a safe temperature range for processing on aluminum foil orhigh-melting-temperature polymer substrates). The processing may occurat various temperatures in the range, such as but not limited to 450° C.In other embodiments, the temperature at the substrate may be betweenabout 400° C. and about 600° C. at the level of the precursor layer, butoptionally cooler at the substrate. The time duration of the processingmay also be reduced by at least about 20% if certain steps are removed.In one embodiment, the heating may occur over a range between about twominutes to about ten minutes. In one embodiment, the processingcomprises heating the precursor layer to a temperature greater thanabout 375° C. but less than a melting temperature of the substrate for aperiod of less than about 15 minutes. In another embodiment, theprocessing comprises heating the precursor layer to a temperaturegreater than about 375° C. but less than a melting temperature of thesubstrate for a period of about 1 minute or less. In a still furtherembodiment, the processing comprises heating the precursor layer to anannealing temperature but less than a melting temperature of thesubstrate for a period of about 1 minute or less. The processing stepmay also be heated and/or accelerated via thermal processing techniquesusing at least one of the following processes: pulsed thermalprocessing, exposure to laser beams, or heating via IR lamps, and/orsimilar or related processes. Although not limited by the following,one-step processes typically occur in a reactive atmosphere, whilemulti-step processes may include one or more steps in non-reactiveatmosphere(s) while the remaining steps are in an reactive atmosphere

The atmosphere associated with the annealing step in FIG. 1C may also bevaried. In one embodiment, the suitable atmosphere comprises anatmosphere containing more than about 10% hydrogen. In anotherembodiment the suitable atmosphere comprises a carbon monoxideatmosphere. However, in other embodiments where very low or no amountsof oxygen are found in the particles, the suitable atmosphere may be anitrogen atmosphere, an argon atmosphere, or an atmosphere having lessthan about 10% hydrogen. These other atmospheres may be advantageous toenable and improve material handling during production.

Although pulsed thermal processing remains generally promising, certainimplementations of the pulsed thermal processing such as a directedplasma arc system, face numerous challenges. In this particular example,a directed plasma arc system sufficient to provide pulsed thermalprocessing is an inherently cumbersome system with high operationalcosts. The direct plasma arc system requires power at a level that makesthe entire system energetically expensive and adds significant cost tothe manufacturing process. The directed plasma arc also exhibits longlag time between pulses and thus makes the system difficult to mate andsynchronize with a continuous, roll-to-roll system. The time it takesfor such a system to recharge between pulses also creates a very slowsystem or one that uses more than one directed plasma arc, which rapidlyincrease system costs.

In some embodiments of the present invention, other devices suitable forrapid thermal processing may be used and they include pulsed lasers usedin adiabatic mode for annealing (Shtyrokov E I, Sov. Phys.—Semicond. 91309), continuous wave lasers (10-30W typically) (Ferris S D 1979Laser-Solid Interactions and Laser Processing (New York: AIP)), pulsedelectron beam devices (Kamins T I 1979 Appl. Phys. Leti. 35 282-5),scanning electron beam systems (McMahon R A 1979 J. Vac. Sci. Techno. 161840-2) (Regolini J L 1979 Appl. Phys. Lett. 34 410), other beam systems(Hodgson R T 1980 Appl. Phys. Lett. 37 187-9), graphite plate heaters(Fan J C C 1983 Mater. Res. Soc. Proc. 4 751-8) (M W Geis 1980 Appl.Phys. Lett. 37 454), lamp systems (Cohen R L 1978 Appl. Phys. Lett. 33751-3), and scanned hydrogen flame systems (Downey D F 1982 Solid StateTechnol. 25 87-93). In some embodiments of the present invention, anon-directed, low density system may be used. Alternatively, other knownpulsed heating processes are also described in U.S. Pat. Nos. 4,350,537and 4,356,384. Additionally, it should be understood that methods andapparatus involving pulsed electron beam processing and rapid thermalprocessing of solar cells as described in expired U.S. Pat. Nos.3,950,187 (“Method and apparatus involving pulsed electron beamprocessing of semiconductor devices”) and 4,082,958 (“Apparatusinvolving pulsed electron beam processing of semiconductor devices”) arein the public domain and well known. U.S. Pat. No. 4,729,962 alsodescribes another known method for rapid thermal processing of solarcells. The above may be applied singly or in single or multiplecombinations with the above or other similar processing techniques withvarious embodiments of the present invention.

It should be noted that using microflakes typically results in precursorlayers that heat into a solid layer at temperatures as much as 50° C.lower than a corresponding layer of spherical nanoparticles. This is duein part because of the greater surface area contact between particles.

In certain embodiments of the invention, the precursor layer 106 (or anyof its sub-layers) may be annealed, either sequentially orsimultaneously. Such annealing may be accomplished by rapid heating ofthe substrate 102 and precursor layer 106 from an ambient temperature toa plateau temperature range of between about 200° C. and about 600° C.In this embodiment of the invention, the temperature may be Processingcomprises annealing with a ramp-rate of 1-5° C./sec, preferably over 5°C./sec, to a temperature of about 200° C. and about 600° C. Thetemperature is maintained in the plateau range for a period of timeranging between about a fraction of a second to about 60 minutes, andsubsequently reduced. Optionally, processing further comprise selenizingthis annealed layer with a ramp-rate of 1-5° C./sec, preferably over 5°C./sec, to a temperature of about 225 to 575° C. for a time period ofabout 60 seconds to about 10 minutes in Se vapor, where the plateautemperature is not necessarily kept constant in time, to form thethin-film containing one or more chalcogenide compounds containing Cu,In, Ga, and Se. Optionally, processing comprises selenizing without theseparate annealing step in an atmosphere containing hydrogen gas, butmay be densified and selenized in one step with a ramp-rate of 1-5C/sec, preferably over 5° C./sec, to a temperature of 225 to 575° C. fora time period of about 120 seconds to about 20 minutes in an atmospherecontaining either H₂Se or a mixture of H₂ and Se vapor.

Alternatively, the annealing temperature could be modulated to oscillatewithin a temperature range without being maintained at a particularplateau temperature. This technique (referred to herein as rapid thermalannealing or RTA) is particularly suitable for forming photovoltaicactive layers (sometimes called “absorber” layers) on metal foilsubstrates, such as but not limited to aluminum foil. Other suitablesubstrates include but are not limited to other metals such as but notlimited to Stainless Steel, Copper, Titanium, or Molybdenum, metallizedplastic foils, glass, ceramic films, and mixtures, alloys, and blends ofthese and similar or related materials. The substrate may be flexible,such as the form of a foil, or rigid, such as the form of a plate, orcombinations of these forms. Additional details of this technique aredescribed in U.S. patent application Ser. No. 10/943,685, which isincorporated herein by reference.

The atmosphere associated with the annealing step may also be varied. Inone embodiment, the suitable atmosphere comprises a hydrogen atmosphere.However, in other embodiments where very low or no amounts of oxygen arefound in the microflakes, the suitable atmosphere may be a nitrogenatmosphere, an argon atmosphere, a carbon monoxide atmosphere, or anatmosphere having less than about 10% hydrogen. These other atmospheresmay be advantageous to enable and improve material handling duringproduction.

Referring now to FIG. 1D, the precursor layer 106 processed in FIG. 1Cwill form a film 110. The film 110 may actually have a reduced thicknesscompared to the thickness of the wet precursor layer 106 since thecarrier liquid and other materials have been removed during processing.In one embodiment, the film 110 may have a thickness in the range ofabout 0.5 microns to about 2.5 microns. In other embodiments, thethickness of film 110 may be between about 1.5 microns and about 2.25microns. In one embodiment, the resulting dense film 110 may besubstantially void free. In some embodiments, the dense film 110 has avoid volume of about 5% or less. In other embodiments, the void volumeis about 10% or less. In another embodiment, the void volume is about20% or less. In still other embodiments, the void volume is about 24% orless. In still other embodiments, the void volume is about 30% or less.The processing of the precursor layer 106 will fuse the particlestogether and in most instances, remove void space and thus reduce thethickness of the resulting dense film.

Depending on the type of materials used to form the film 110, the film110 may be suitable for use as an absorber layer or be further processedto become an absorber layer. More specifically, the film 110 may be afilm as a result of a one step process, or for use in another subsequentone step process making it a two step process, or for use in amulti-step process. In a one step process, the film 110 is formed toinclude group IB-IIIA-VIA compounds and the film 110 may be an absorberfilm suitable for use in a photovoltaic device. In a two step process,the film 110 may be a solid and/or densified film that will have furtherprocessing to be suitable for use as an absorber film for use in aphotovoltaic device. As a nonlimiting example, the film 110 in a twostep process may not contain any and/or sufficient amounts of a groupVIA element to function as an absorber layer. Adding a group VIA elementor other material may be the second step of the two-step process. Eithera mixture of two or more VIA elements can be used, or a third step canbe added with another VIA element as used in the second step. A varietyof methods of adding that material include printing of group VIAelement, using VIA element vapor, and/or other techniques. It shouldalso be understood that in a two step process, the process atmospheresmay be different. By way of nonlimiting example, one atmosphere mayoptionally be a group VIA-based atmosphere. As another nonlimitingexample, one atmosphere may be an inert atmosphere as described herein.Other processing steps as used in a multi-step process may be a wetchemical surface treatment to improve the IB-IIIA-VIA thin-film surface,and/or an additional rapid thermal heating to improve bulk and surfaceproperties of the IB-IIIA-VIA thin-film.

Optionally, the present invention may comprise of adding a material tosolidify micron-sized or larger feedstock (to be used to preparesub-micron or nano-sized particles), that otherwise would be all orpartially liquid at particle preparation, handling, or deposition orpre-deposition temperature. In another embodiment, the present inventionmay comprise of adding material to solidify sub-micron or nano-sizedglobules/droplets, that otherwise would be all or partially liquid atparticle preparation, handling, or deposition or pre-depositiontemperature. All combinations of size (large feedstock and sub-micron),process temperature (particle preparation, ink and web handling, anddeposition), and timing (before size reduction, after size reduction)are considered herein.

Microflakes

Referring now to FIGS. 2A and 2B, embodiments of the microflakes 108according to the present invention will be described in further detail.The microflakes 108 may come in a variety of shapes and sizes. In oneembodiment, the microflakes 108 may have a large aspect ratio, in termsof particle thickness to particle length. FIG. 2A shows that somemicroflakes have thicknesses between about 0.2 to about 0.4 microns (200to 400 nm) and lengths between about 2 to about 5 microns (2000 to 5000nm). As a nonlimiting example, the plates are thin (about 100 nm to 75nm thickness or less) while their lengths may be as large as about 5microns (5000 nm). Some may have a length of about 3 microns (3000 nm)or less. Other embodiments of the microflakes 108 may have a length ofabout 1 micron (1000 nm) or less. The aspect ratio in some embodimentsof microflakes may be about 10:1 or more (ratio of the longest dimensionto the shortest dimension of a particle). Other embodiments may have anaspect ratio of about 30:1 or more. Still others may have an aspectratio of about 50:1 or more. An increase in aspect ratio would indicatethat the longest dimension has increased over the shortest dimension orthat the shortest dimension has decreased relative to the longestdimension. Thus, aspect ratio herein involves the longest lateraldimension (be it length or width) relative to the shortest dimension,which is typically the thickness of a flake. The dimensions are measuredalong edges or across a major axis to provide measurement of dimensionssuch as but not limited to length, width, depth, and/or diameter. Whenreferring to a plurality of microflakes having a defined aspect ratio,what is meant is that all of the microflakes of a composition as a wholehave an average aspect ratio as defined. It should be understood thatthere may be a distribution of particle aspect ratios around the averageaspect ratio.

As seen in FIG. 2A, although the size and shape of the microflakes 108may vary, most include at least one substantially planar surface 120.The at least one planar surface 120 allows for greater surface contactbetween adjacent microflakes 108. The greater surface contact provides avariety of benefits. The greater contact allows for improved atomicintermixing between adjacent particles. For microflakes containing morethan one element, even though there may be atomic intermixing already inplace for the particles, the close contact in the film allows easysubsequent diffusion. Thus, if a particle is slightly rich in oneelement, the increased contact facilitates a more even distribution ofelements in the resulting dense film. Furthermore, greater interparticleinterfacial area leads to faster reaction rates. The planar shape of theparticles maximizes interparticle contact area. The interparticlecontact area allows chemical reactions (e.g. based for example uponatomic diffusion) to be initiated, catalyzed, and/or progress relativelyrapidly and concurrently over large areas. Thus, not only does the shapeimprove intermixing, the greater interfacial area and interparticlecontact area also improves reaction rates.

Referring still to FIG. 2A, the planar shape also allows for improvedpacking density. As seen in FIG. 2A, the microflakes 108 may be orientedsubstantially parallel to the surface of substrate 102 and stack one ontop of the other to form the precursor layer 106. Intrinsically, thegeometry of the microflakes allow for more intimate contact thanspherical particles or nanoparticles in the precursor layer. In fact, itis possible that 100% of the planar surface of the microflake is incontact with another microflake. Thus, the planar shape of themicroflakes creates a higher packing density in the dense film ascompared to a film made from a precursor layer using an ink of sphericalnanoparticles of the same composition that is otherwise substantiallyidentical. In some embodiments, the planar shape of the microflakescreates a packing density of at least about 70% in the precursor layer.In other embodiments, the microflakes create a packing density of atleast about 80% in the precursor layer. In other embodiments, themicroflakes create a packing density of at least about 90% in theprecursor layer. In other embodiments, the microflakes create a packingdensity of at least about 95% in the precursor layer.

As seen in FIG. 2B, the microflakes 108 may have a variety of shapes. Insome embodiments, the microflakes in the ink may include those that areof random size and/or random shape. On the contrary, particles size isextremely important for standard spherical nanoparticles, and thosespherical nanoparticles of different size and composition will result indispersion with unstable atomic composition. The planar surface 120 ofthe microflakes allows for particles that are more easily suspended inthe carrier liquid. Thus, even though the microflakes may not bemonodisperse in size, putting the constituent metals in plate formprovides one method to have particles suspended in the carrier liquidwithout rapid and/or preferential settling of any constituent element.

It should be understood that the microflakes 108 of the presentinvention may be formed and/or size discriminated to provide a morecontrolled size and shape distribution. The size distribution ofmicroflakes may be such that one standard deviation from a mean lengthand/or width of the microflakes is less than about 1000 nm. The sizedistribution of microflakes may be such that one standard deviation froma mean length and/or width of the microflakes is less than about 600 nm.The size distribution of microflakes may be such that one standarddeviation from a mean length and/or width of the microflakes is lessthan about 500 nm. The size distribution of microflakes may be such thatone standard deviation from a mean length and/or width of themicroflakes is less than about 400 nm. The size distribution ofmicroflakes may be such that one standard deviation from a mean lengthand/or width of the microflakes is less than about 250 nm. In anotherembodiment, the size distribution of microflakes may be such that onestandard deviation from a mean length and/or width of the microflakes isless than about 100 nm.

In another embodiment, one standard deviation from a mean length of themicroflakes is less than about 50 nm.

In yet another embodiment, one standard deviation from a mean thicknessof the microflakes is less than about 10 nm. In another embodiment ofthe invention, one standard deviation from a mean thickness of themicroflakes is less than about 5 nm. The microflakes each have athickness less than about 250 nm. In another embodiment, the microflakeseach have a thickness less than about 100 nm. In yet another embodiment,the microflakes each have a thickness less than about 20 nm. Themicroflakes may have a length of less than about 5 microns and athickness of less than about 250 nm. In another embodiment, themicroflakes may have a length of less than about 2 microns and athickness of less than about 100 nm. In another embodiment, themicroflakes have a length of less than about 1 micron and a thickness ofless than about 50 nm. In terms of their shape, the microflakes may havean aspect ratio of at least about 10 or more. In another embodiment, themicroflakes have an aspect ratio of at least about 15 or more. Themicroflakes are of random planar shape and/or a random sizedistribution. In other embodiments, the microflakes are of non-randomplanar shape and/or a non-random size distribution. Additionally, FIG.2C shows a magnified top-down view of nanoflakes 121 according to oneembodiment of the present invention

The stoichiometric ratio of elements may vary between individualmicroflakes so long as the overall amount in all of the particlescombined is at the desired or close to the desired stoichiometric ratiofor the precursor layer and/or resulting dense film. According to onepreferred embodiment of that process, the overall amount of elements inthe resulting film has a Cu/(In+Ga) compositional range of about 0.7 toabout 1.0 and a Ga/(In+Ga) compositional range of about 0.05 to about0.30. Optionally, the Se/(In+Ga) compositional range may be about 0.00to about 4.00 such that a later step involving use of an additionalsource of Se may or may not be required.

Microflake Formation

Referring now to FIG. 3, one embodiment of a device for formingmicroflakes 108 will now be described. Microflakes 108 may be obtainedby a variety of techniques including, but not limited to, size reducingtechniques like mortar and pestle technology, bean blasting, ballmilling, bead milling, small media milling, agitator ball milling,planetary milling, horizontal ball milling, pebble milling, pulverizing,hammering, dry grinding, wet grinding, jet milling, or other types ofmilling, applied singly or in any combination, on a commerciallyavailable feedstock of the desired elemental, binary, ternary, ormulti-nary material. FIG. 3 shows one embodiment of a milling system 130using a milling machine 132 that contains the balls or beads, or othermaterial used in the milling process. The system 130 may be a closedsystem to provide an oxygen-free environment for processing of thefeedstock material. A source of inert or reducing gas 134 may be coupledto the closed system to maintain an oxygen-free environment. The millingsystem 130 may also be configured to allow for cryomilling by providinga liquid nitrogen or other cooling source 136 (shown in phantom).Alternatively, the milling system 130 may also be configured to provideheating during the milling process. Cycles of heating and/or cooling canalso be carried out during the milling process. Optionally, the millingmay also involve mixing a carrier liquid and/or a dispersing agent withthe powder or feedstock being processed. To prevent or reverseoxidation, inhibitors or reducing agents can be added to the mill withthe rest of the components of the ink. This inhibitor may remain withthe ink or remain with the media which is filtered out of the ink. Inone embodiment of the present invention, the microflakes 108 created bymilling may be of a variety of sizes such as but not limited to, about20 nanometers to about 500 nanometers in thickness. In anotherembodiment, the microflakes may be between about 75 nanometers to 100nanometers in thickness.

It should be understood that the milling may use beads or microbeadsmade of materials harder and/or having a higher mass density than thefeedstock particles to transform the feedstock particles to theappropriate size and shape. In one embodiment, these beads are glass,ceramic, alumina, porcelain, silicon carbide, or tungsten carbide beads,stainless steel balls with ceramic shells, iron balls with ceramicshells, or the like to minimize contamination risk to the microflakes.The mill itself or parts of the mill may also have a ceramic lining or alining of another inert material or parts of the mill may be completelyceramic or made chemically and mechanically inert to minimizecontamination of the slurry containing the microflakes. The beads mayalso be sieved regularly during the process.

The ball milling may occur in an oxygen-free environment. This mayinvolve using a mill that is sealed from the outside environment andpurged of air. Milling may then occur under an inert atmosphere or otheroxygen-free environment. Some embodiments may involve placing the millinside a hood or chamber that provides the sealing for an oxygen-freeenvironment. The process may involve drying and degassing the vehicle orchoosing anhydrous, oxygen-free solvent to begin with and loadingwithout contact to air. The oxygen-free milling may create oxygen-freemicroflakes which in turn reduces the need for a step to remove oxygenfrom the particles. This could significantly reduce the anneal timeassociated with turning the microflakes precursor layer into the densefilm. In some embodiments, the anneal time is in the range of about 30seconds. Related to air-free microflake creation (size reduction), itshould be understood that the present invention may also includeair-free dispersion creation, and air-free coating, storage and/orhandling.

The milling may occur at a variety of temperatures. In one embodiment ofthe present invention, the milling occurs at room temperature. Inanother embodiment, the milling occurs at a cryogenic temperature suchas but not limited to ≦−175° C. This may allow milling to work onparticles that may be liquid or not sufficiently brittle at roomtemperature for size reduction. The milling may also occur at a desiredmilling temperature wherein all precursor particles are solids and theprecursor particles have a sufficient malleability at the millingtemperature to form the planar shape from the non-planar or planarstarting shape. This desired temperature may be at room temperature,above room temperature, or below room temperature, and/or cycle betweenvarious temperatures. In one embodiment, the milling temperature may beless than about 15 degrees C. In another embodiment, the temperature isat less than about −175 degrees C. In yet another embodiment, themilling may be cooled by liquid nitrogen which is 80K, being −193° C.Temperature control during milling may control possible chemicalreaction between solvent, dispersant, feedstock material, and/or partsof the mill. It should be understood that in addition to theaforementioned, the temperature may also vary over different timeperiods of the milling process. As a nonlimiting example, the millingmay occur at a first temperature over an initial milling time period andproceed to other temperatures for subsequent time periods during themilling.

The milling may transform substantially all of the precursor particlesinto microflakes. In some embodiments, the milling transforms at leastabout 50% (by weight of all of the precursor particles) of the precursorparticles into microflakes. Additionally, it should be understood thatthe temperature can be constant or changed during milling. This may beuseful to adjust the material properties of the feedstock material orpartially milled material to create particles of desired shape, size,and/or composition.

Although the present invention discloses a “top down” method for formingmicroflakes, it should be understood that other techniques may also beused. For example, quenching a material from the melt on a surface suchas a liquid cooling bath. Indium (and likely gallium and selenium)microflakes may be formed by emulsifying molten indium while agitatingand quenching at the surface of a cooling bath. It should be understoodthat any wet chemical, dry chemical, dry physical, and/or wet physicaltechnique to make flakes can be used with the present invention (apartfrom dry or wet size reduction). Thus, the present invention is notlimited to wet physical top-down methods (milling), but may also includedry/wet bottom-up approaches. It should also be noted that sizereduction may optionally be a multi-step process. In one nonlimitingexample, this may first involve taking mm-sized chunks/pieces that aredry grinded to <100 um, subsequently milled in one, two, three, or moresteps with subsequent reducing bead size to the microflakes.

It should be understood that the feedstock particles for use with thepresent invention may be prepared by a variety of methods. By way ofexample and not limitation, U.S. Pat. No. 5,985,691 issued to B. M.Basol et al describes a particle-based method to form a GroupIB-IIIA-VIA compound film. Eberspacher and Pauls in U.S. Pat. No.6,821,559 describe a process for making phase-stabilized precursors inthe form of fine particles, such as sub-micron multinary metalparticles, and multi-phase mixed-metal particles comprising at least onemetal oxide. Bulent Basol in U.S. Published Patent application number20040219730 describes a process of forming a compound film includingformulating a nano-powder material with a controlled overall compositionand having particles of one solid solution. Using the solid-solutionapproach, Gallium can be incorporated into the metallic dispersion innon-oxide form—but only with up to approximately 18 relative atomicpercent (Subramanian, P. R. and Laughlin, D. E., in Binary Alloy PhaseDiagrams, 2^(nd) Edition, edited by Massalski, T. B. 1990. ASMinternational, Materials Park, Ohio, pp 1410-1412; Hansen, M.,Constitution of Binary Alloys. 1958. 2^(nd) Edition, McGraw Hill, pp.582-584.) U.S. patent application Ser. No. 11/081,163 describes aprocess of forming a compound film by formulating a mixture of elementalnanoparticles composed of the IB, the IIIA, and, optionally, the VIAgroup of elements having a controlled overall composition. Discussion onchalcogenide powders may also be found in the following: [(1) Vervaet,A. et al., E. C. Photovoltaic Sol. Energy Conf., Proc. Int. Conf., 10th(1991), 900-3.; (2) Journal of Electronic Materials, Vol. 27, No. 5,1998, p. 433; Ginley et al.; (3) WO 99,378,32; Ginley et al.; (4) U.S.Pat. No. 6,126,740]. These methods may be used to create feedstock to besize reduced. Others may form precursor sub-micron-sized particles readyfor solution-deposition. All documents listed above are fullyincorporated herein by reference for all purposes.

Ink Preparation

To formulate the dispersion used in the precursor layer 106, themicroflakes 108 are mixed together and with one or more chemicalsincluding but not limited to dispersants, surfactants, polymers,binders, cross-linking agents, emulsifiers, anti-foaming agents, dryers,solvents, fillers, extenders, thickening agents, film conditioners,anti-oxidants, flow agents, leveling agents, and corrosion inhibitors,oxidation inhibitors, and reducing agents.

The inks created using the present invention may optionally include adispersant. Some embodiments may not include any dispersants.Dispersants (also called wetting agents) are surface-active substancesused to prevent particles from aggregating or flocculating, thusfacilitating the suspension of solid materials in a liquid medium andstabilizing the dispersion thereby produced. If particle surfacesattract one another, then flocculation occurs, often resulting inaggregation and decreasing stability and/or homogeneity. If particlesurfaces repel one another, then stabilization occurs, where particlesdo not aggregate and tend not to settle out of solution as fast.

An efficient dispersing agent can typically perform pigment wetting,dispersing, and stabilizing. Examples of dispersing agents arepolyphosphates, styrene-maleinates, polyacrylates, polyacids, glycolethers, alkyl/alkoxy-substituted amines (ternary and quaternary) andamides, and polyethyle/polypropylene glycol-containing molecules, areoften used for aqueous formulations whereas fatty acid derivatives, andlow molecular weight modified alkyd and polyester resins are often usedfor organic formulations. In one nonlimiting embodiment, the dispersingagent may be 0.5% to 4% by weight dispersant (ratio todispersant+particle weight) such as triethanol-amine (TEA) with 30% byweight of solvent (solvent+particle weight) such as iso-propyl-alcohol.

Surfactants are surface-active agents that lower the surface tension ofthe solvent in which they dissolve, serving as wetting agents, andkeeping the surface tension of an (aqueous) medium low so that an inkinteracts with a substrate surface. Certain types of surfactants arealso used as dispersing agents. Surfactants typically contain both ahydrophobic carbon chain and a hydrophilic polar group. The polar groupcan be non-ionic. If the polar group is ionic, the charge can be eitherpositive or negative, resulting in cationic or anionic surfactants.Zwitterionic surfactants contain both positive and negative chargeswithin the same molecule; one example is N-n-Dodecyl-N,N-dimethylbetaine. Certain surfactants are often used as dispersant agents foraqueous solutions. Representative classes include acetylene diols, fattyacid derivatives, phosphate esters, sodium polyacrylate salts,polyacrylic acids, soya lecithin, trioctylphosphine (TOP), andtrioctylphosphine oxide (TOPO).

Binders and resins are often used to hold together proximate particlesin a nascent or formed dispersion. Examples of typical binders includeacrylic monomers (both as monofunctional diluents and multifunctionalreactive agents), acrylic resins (e.g. acrylic polyol, amine synergists,epoxy acrylics, polyester acrylics, polyether acrylics,styrene/acrylics, urethane acrylics, or vinyl acrylics), alkyd resins(e.g. long-oil, medium-oil, short-oil, or tall oil), adhesion promoterssuch as but not limited to polyvinyl pyrrolidone (PVP), amide resins,amino resins (such as but not limited to melamine-based or urea-basedcompounds), asphalt/bitumen, butadiene acrylonitriles, cellulosic resins(such as but not limited to cellulose acetate butyrate (CAB)), celluloseacetate proprionate (CAP), ethyl cellulose (EC), nitrocellulose (NC), ororganic cellulose ester), chlorinated rubber, dimer fatty acids, epoxyresin (e.g. acrylates, bisphenol A-based resins, epoxy UV curing resins,esters, phenol and cresol (Novolacs), or phenoxy-based compounds),ethylene co-terpolymers such as ethylene acrylic/methacrylic Acid, E/AA,E/M/AA or ethylene vinyl acetate (EVA), fluoropolymers, gelatin (e.g.Pluronic F-68 from BASF Corporation of Florham Park, N.J.), glycolmonomers, hydrocarbon resins (e.g. aliphatic, aromatic, orcoumarone-based such as indene), maelic resins, modified urea, naturalrubber, natural resins and gums, rosins, modified phenolic resins,resols, polyamide, polybutadienes (liquid hydroxyl-terminated),polyesters (both saturated and unsaturated), polyolefins, polyurethane(PU) isocyanates (e.g. hexamethylene diisocynate (HDI), isophoronediisocyanate (IPDI), cycloaliphatics, diphenylmethane disiocyanate(MDI), toluene diisocynate (TDI), or trimethylhexamethylene diisocynate(TMDI)), polyurethane (PU) polyols (e.g. caprolactone, dimer-basedpolyesters, polyester, or polyether), polyurethane (PU) dispersions(PUDs) such those based on polyesters or polyethers, polyurethaneprepolymers (e.g. caprolactone, dimer-based polyesters, polyesters,polyethers, and compounds based on urethane acrylate), Polyurethanethermoplastics (TPU) such as polyester or polyether, silicates (e.g.alkyl-silicates or water-glass based compounds), silicones (aminefunctional, epoxy functional, ethoxy functional, hydroxyl functional,methoxy functional, silanol functional, or cinyl functional), styrenes(e.g. styrene-butadiene emulsions, and styrene/vinyl toluene polymersand copolymers), or vinyl compounds (e.g. polyolefins and polyolefinderivatives, polystyrene and styrene copolymers, or polyvinyl acetate(PVAC)).

Emulsifiers are dispersing agents that blend liquids with other liquidsby promoting the breakup of aggregating materials into small dropletsand therefore stabilize the suspension in solution. For example,sorbitan esters are used as an emulsifier for the preparation ofwater-in-oil (w/o) emulsions, for the preparation of oil absorptionbases (w/o), for the formation of w/o type pomades, as a reabsorptionagent, and as a non toxic anti-foaming agent. Examples of emulsifiersare sorbitan esters such as sorbitan sesquioleate (Arlacel 60), sorbitansesquioleate (Arlacel 83), sorbitan monolaurate (Span 20), sorbitanmonopalmitate (Span 40), sorbitan monostearate (Span 60), sorbitantristearate (Span 65), sorbitan mono-oleate (Span 80), and sorbitantrioleate (Span 85) all of which are available, e.g., from Uniqema ofNew Castle, Del. Other polymeric emulsifiers include polyoxyethylenemonostearate (Myrj 45), polyoxyethylene monostearate (Myrj 49), polyoxyl40 stearate (Myrj 52), polyoxyethylene monolaurate (PEG 400),polyoxyethylene monooleate (PEG 400 monoleate) and polyoxyethylenemonostearate (PEG 400 monostearate), and the Tween series of surfactantsincluding but not limited to polyoxyethylene sorbitan monolaurate (Tween20), polyoxyethylene sorbitan monolaurate (Tween 21), polyoxyethylenesorbitan monopalmitate (Tween 40), polyoxyethylene sorbitan monostearate(Tween 60), polyoxyethylene sorbitan tristearate (Tween 61),polyoxyethylene sorbitan mono-oleate (Tween 80), polyoxyethylenesorbitan monooleate (Tween 81), and polyoxyethylene sorbitan tri-oleate(Tween 85) all of which are available, e.g., from Uniqema of New Castle,Del. Arlacel, Myrj, and Tween are registered trademarks of ICI AmericasInc. of Wilmington, Del. Emulsifiers are not limited to this commonlist. In fact dispersing agents (some examples found above) for asolid-liquid system might work as suitable emulsifiers for acorresponding liquid-liquid system.

Foam may form during the coating/printing process, especially if theprinting process takes place at high speeds. Surfactants may adsorb onthe liquid-air interface and stabilize it, accelerating foam formation.Anti-foaming agents prevent foaming from being initiated, whiledefoaming agents minimize or eliminate previously-formed foam.Anti-foaming agents include hydrophobic solids, fatty oils, and certainsurfactants, all of which penetrate the liquid-air interface to slowfoam formation. Anti-foaming agents also include both silicate, siliconeand silicone-free materials. Silicone-free materials includemicrocrystalline wax, mineral oil, polymeric materials, and silica- andsurfactant-based materials.

Solvents can be aqueous (water-based) or non-aqueous (organic). Whileenvironmentally friendly, water-based solutions carry the disadvantageof a relatively higher surface tension than organic solvents, making itmore difficult to wet substrates, especially plastic substrates. Toimprove substrate wetting with polymer substrates, surfactants may beadded to lower the ink surface tension (while minimizingsurfactant-stabilized foaming), while the substrate surfaces aremodified to enhance their surface energy (e.g. by corona treatment).Typical organic solvents include acetate, acrylates, alcohols (butyl,ethyl, isopropyl, or methyl), aldehydes, benzene, dibromomethane,chloroform, dichloromethane, dichloroethane, trichloroethane, cycliccompounds (e.g. cyclopentanone or cyclohexanone), esters (e.g. butylacetate or ethyl acetate), ethers, glycols (such as ethylene glycol orpropylene glycol), hexane, heptane, aliphatic hydrocarbons, aromatichydrocarbons, ketones (e.g. acetone, methyl ethyl ketone, or methylisobutyl ketone), natural oils, terpenes, terpinol, toluene.

Additional components may include fillers/extenders, thickening agents,rheology modifiers, surface conditioners, including adhesionpromoters/bonding, anti-gelling agents, anti-blocking agents, antistaticagents, chelating/complexing agents, corrosion inhibitors, flame/rustinhibitors, flame and fire retardants, humectants, heat stabilizers,light-stabilizers/UV absorbers, lubricants, pH stabilizers, andmaterials for slip control, anti-oxidants, reducing agents, and flow andleveling agents. It should be understood that all components may beadded singly or in combination with other components.

Roll-to-Roll Manufacturing

Referring now to FIG. 4, a roll-to-roll manufacturing process accordingto the present invention will now be described. Embodiments of theinvention using the microflakes are well suited for use withroll-to-roll manufacturing. Specifically, in a roll-to-rollmanufacturing system 200 a flexible substrate 201, e.g., aluminum foiltravels from a supply roll 202 to a take-up roll 204. In between thesupply and take-up rolls, the substrate 201 passes a number ofapplicators 206A, 206B, 206C, e.g. microgravure rollers and heater units208A, 208B, 208C. Each applicator deposits a different layer orsub-layer of a precursor layer, e.g., as described above. The heaterunits are used to anneal the different layers and/or sub-layers to formdense films. In the example depicted in FIG. 4, applicators 206A and206B may apply different sub-layers of a precursor layer (such asprecursor layer 106). Heater units 208A and 208B may anneal eachsub-layer before the next sub-layer is deposited. Alternatively, bothsub-layers may be annealed at the same time. Applicator 206C mayoptionally apply an extra layer of material containing chalcogen oralloy or elemental particles as described above. Heater unit 208C heatsthe optional layer and precursor layer as described above. Note that itis also possible to deposit the precursor layer (or sub-layers) thendeposit any additional layer and then heat all three layers together toform the IB-IIIA-chalcogenide compound film used for the photovoltaicabsorber layer. The roll-to-roll system may be a continuous roll-to-rolland/or segmented roll-to-roll, and/or batch mode processing.

Photovoltaic Device

Referring now to FIG. 5, the films fabricated as described above mayserve as an absorber layer in a photovoltaic device, module, or solarpanel. An example of such a photovoltaic device 300 is shown in FIG. 4.The device 300 includes a base substrate 302, an optional adhesionand/or barrier layer 303, a base or back electrode 304, a p-typeabsorber layer 306 incorporating a film of the type described above, an-type semiconductor thin film 308 and a transparent electrode 310. Byway of example, the base substrate 302 may be made of a metal foil, apolymer such as polyimides (PI), polyamides, polyetheretherketone(PEEK), Polyethersulfone (PES), polyetherimide (PEI), polyethylenenaphtalate (PEN), Polyester (PET), related polymers, or a metallizedplastic. By way of nonlimiting example, related polymers include thosewith similar structural and/or functional properties and/or materialattributes. The base electrode 304 is made of an electrically conductivematerial. By way of example, the base electrode 304 may be of a metallayer whose thickness may be selected from the range of about 0.1 micronto about 25 microns.

An optional intermediate layer 303 may be incorporated between theelectrode 304 and the substrate 302. The transparent electrode 310 mayinclude a transparent conductive layer 309 and a layer of metal (e.g.,Al, Ag, Cu, or Ni) fingers 311 to reduce sheet resistance.

Optionally, the layer 303 may be a diffusion barrier layer to preventdiffusion of material between the substrate 302 and the electrode 304.Aluminum and molybdenum can and often do inter-diffuse into one another,especially upon heating to elevated temperatures as used for absorbergrowth, with deleterious electronic and/or optoelectronic effects on thedevice 300. Furthermore aluminum can diffuse though molybdenum intolayers beyond e.g. CIG(S). To inhibit such inter-diffusion, anintermediate, interfacial layer 303 may be incorporated between thealuminum foil substrate 302 and molybdenum base electrode 304. Theinterfacial layer may be composed of any of a variety of materials,including but not limited to chromium, vanadium, tungsten, and glass, orcompounds such as nitrides (including but not limited to titaniumnitride, tantalum nitride, tungsten nitride, hafnium nitride, niobiumnitride, zirconium nitride, vanadium nitride, silicon nitride, ormolybdenum nitride), oxynitrides (including but not limited tooxynitrides of Ti, Ta, V, W, Si, Zr, Nb, Hf, or Mo), oxides, and/orcarbides. The material may be selected to be an electrically conductivematerial. In one embodiment, the materials selected from theaforementioned may be those that are electrically conductive diffusionbarriers. The thickness of this layer can range from 10 nm to 50 nm orfrom 10 nm to 30 nm. Optionally, the thickness may be in the range ofabout 50 nm to about 1000 nm. Optionally, the thickness may be in therange of about 100 nm to about 750 nm. Optionally, the thickness may bein the range of about 100 nm to about 500 nm. Optionally, the thicknessmay be in the range of about 110 nm to about 300 nm. In one embodiment,the thickness of the layer 303 is at least 100 nm or more. In anotherembodiment, the thickness of the layer 303 is at least 150 nm or more.In one embodiment, the thickness of the layer 303 is at least 200 nm ormore. Optionally, some embodiments may include another layer such as butnot limited to a copper layer, a titanium layer, or other metal layerabove the layer 303 and below the base electrode layer 304. Optionally,some embodiments may include another layer such as but not limited to acopper layer, a titanium layer, an aluminum layer, or other metal layerbelow the layer 303 and below the base electrode layer 304. This layermay be thicker than the layer 303. Optionally, it may be the samethickness or thinner than the layer 303. This layer 303 may be placed onone or optionally both sides of the aluminum foil (shown as layer 305 inphantom in FIG. 5).

If barrier layers are on both sides of the aluminum foil, it should beunderstood that the protective layers may be of the same material orthey may optionally be different materials from the aforementionedmaterials. The bottom protective layer 305 may be any of the materials.Optionally, some embodiments may include another layer 307 such as butnot limited to an aluminum layer above the layer 305 and below thealuminum foil 302. This layer 307 may be thicker than the layer 303.

The transparent electrode 310 may include a transparent conductive layer309 and a layer of metal (e.g., Al, Ag, Cu, or Ni) fingers 311 to reducesheet resistance. The n-type semiconductor thin film 308 serves as ajunction partner between the compound film and the transparentconducting layer 309. By way of example, the n-type semiconductor thinfilm 308 (sometimes referred to as a junction partner layer) may includeinorganic materials such as cadmium sulfide (CdS), zinc sulfide (ZnS),zinc hydroxide, zinc selenide (ZnSe), n-type organic materials, or somecombination of two or more of these or similar materials, or organicmaterials such as n-type polymers and/or small molecules. Layers ofthese materials may be deposited, e.g., by chemical bath deposition(CBD) and/or chemical surface deposition (and/or related methods), to athickness ranging from about 2 nm to about 1000 nm, more preferably fromabout 5 nm to about 500 nm, and most preferably from about 10 nm toabout 300 nm. This may also configured for use in a continuousroll-to-roll and/or segmented roll-to-roll and/or a batch mode system.

The transparent conductive layer 309 may be inorganic, e.g., atransparent conductive oxide (TCO) such as but not limited to indium tinoxide (ITO), fluorinated indium tin oxide, zinc oxide (ZnO) or aluminumdoped zinc oxide, or a related material, which can be deposited usingany of a variety of means including but not limited to sputtering,evaporation, chemical bath deposition (CBD), electroplating, sol-gelbased coating, spray coating, chemical vapor deposition (CVD), physicalvapor deposition (PVD), atomic layer deposition (ALD), and the like.Alternatively, the transparent conductive layer may include atransparent conductive polymeric layer, e.g. a transparent layer ofdoped PEDOT (Poly-3,4-Ethylenedioxythiophene), carbon nanotubes orrelated structures, or other transparent organic materials, eithersingly or in combination, which can be deposited using spin, dip, orspray coating, and the like or using any of various vapor depositiontechniques. Optionally, it should be understood that intrinsic(non-conductive layer such as intrinsic ZnO ( ) i-ZnO) may be usedbetween CdS and Al-doped ZnO. Optionally, an insulating layer may beincluded between the layer 308 and transparent conductive layer 309.Combinations of inorganic and organic materials can also be used to forma hybrid transparent conductive layer. Thus, the layer 309 mayoptionally be an organic (polymeric or a mixed polymeric-molecular) or ahybrid (organic-inorganic) material.). Examples of such a transparentconductive layer are described e.g., in commonly-assigned US PatentApplication Publication Number 20040187917, which is incorporated hereinby reference.

Those of skill in the art will be able to devise variations on the aboveembodiments that are within the scope of these teachings. For example,it is noted that in embodiments of the present invention, portions ofthe IB-IIIA precursor layers (or certain sub-layers of the precursorlayers or other layers in the stack) may be deposited using techniquesother than microflake-based inks. For example precursor layers orconstituent sub-layers may be deposited using any of a variety ofalternative deposition techniques including but not limited tosolution-deposition of spherical nanopowder-based inks, vapor depositiontechniques such as ALD, evaporation, sputtering, CVD, PVD,electroplating and the like.

Referring now to FIG. 6, a flowchart showing one embodiment of a methodaccording to the present invention will now be described. FIG. 6 showsthat at step 350, the microflakes 108 may be created using one of theprocesses described herein. Optionally, there may be a washing step 351to remove any undesired residue. Once the microflakes 108 are created,step 352 shows that the ink may be formulated with the microflakes andat least one other component such as but not limited to a carrierliquid. Optionally, it should be understood that some embodiments of theinvention may combine the steps 350 and 352 into one process step asindicated by box 353 (shown in phantom) if the creation process resultsin a coatable formulation. As one nonlimiting example, this may be thecase if the dispersants and/or solvents used during formation can alsobe used to form a good coating. At step 354, the substrate 102 may becoated with the ink to form the precursor layer 106. Optionally, theremay be a step 355 of removing dispersant and/or other residual of theas-coated layer 106 by methods such as but not limited to heating,washing, or the like. Optionally, step 355 may involve a step ofremoving solve after ink deposition by using a drying device such as butnot limited to a drying tunnel/furnace. Step 356 shows the precursorlayer is processed to form a dense film which may then further beprocessed at step 358 to form the absorber layer. Optionally, it shouldbe understood that some embodiments of the invention may combine thesteps 356 and 358 into one process step if the dense film is an absorberlayer and no further processing of the film is needed. Step 360 showsthat the n-type junction may be formed over and/or in contact with theabsorber layer. Step 362 shows that a transparent electrode may beformed over the n-type junction layer to create a stack that canfunction as a solar cell.

Referring now to FIG. 7, it should also be understood that a pluralityof devices 300 may be incorporated into a module 400 to form a solarmodule that includes various packaging, durability, and environmentalprotection features to enable the devices 300 to be installed in anoutdoor environment. In one embodiment, the module 400 may include aframe 402 that supports a substrate 404 on which the devices 300 may bemounted. This module 400 simplifies the installation process by allowinga plurality of devices 300 to be installed at one time. Alternatively,flexible form factors may also be employed. It should also be understoodthat an encapsulating device and/or layers may be used to protect fromenvironmental influences. As a nonlimiting example, the encapsulatingdevice and/or layers may block the ingress of moisture and/or oxygenand/or acidic rain into the device, especially over extendedenvironmental exposure.

Extra Source of Chalcogen

It should be understood that the present invention using microflakes mayalso use an extra chalcogen source in a manner similar to that describedin copending, U.S. patent application Ser. No. 11/290,633, wherein theprecursor material contains 1) chalcogenides such as, but not limitedto, copper selenide, and/or indium selenide and/or gallium selenideand/or 2) a source of extra chalcogen such as, but not limited to, Se orS nanoparticles less than about 200 nanometers in size. In onenonlimiting example, the chalcogenide and/or the extra chalcogen may bein the form of microflakes and/or nanoflakes while the extra source ofchalcogen may be flakes and/or non-flakes. The chalcogenide microflakesmay be one or more binary alloy chalcogenides such as, but not limitedto, group IB-binary chalcogenide nanoparticles (e.g. group IB non-oxidechalcogenides, such as Cu—Se, Cu—S or Cu—Te) and/or groupIIIA-chalcogenide nanoparticles (e.g., group IIIA non-oxidechalcogenides, such as Ga(Se, S, Te), In(Se, S, Te) and Al(Se, S, Te).In other embodiments, the microflakes may be non-chalcogenides such asbut not limited to group IB and/or IIIA materials like Cu—In, Cu—Ga,and/or In—Ga. If the chalcogen melts at a relatively low temperature(e.g., 220° C. for Se, 120° C. for S) the chalcogen is already in aliquid state and makes good contact with the microflakes. If themicroflakes and chalcogen are then heated sufficiently (e.g., at about375° C.), the chalcogen reacts with the chalcogenides to form thedesired IB-IIIA-chalcogenide material.

Referring now to FIGS. 8A-8C, the chalcogenide microflakes 502 and asource of extra chalcogen, e.g., in the form of a powder containingchalcogen particles 504 may be supported on a substrate 501. As anonlimiting example, the chalcogen particles may be micron- and/orsubmicron-sized non-oxygen chalcogen (e.g., Se, S or Te) particles,e.g., a few hundred nanometers or less to a few microns in size. Themixture of chalcogenide microflakes 502 and chalcogen particles 504 isplaced on the substrate 501 and heated to a temperature sufficient tomelt the extra chalcogen particles 504 to form a liquid chalcogen 506 asshown in FIG. 8B. The liquid chalcogen 506 and chalcogenides 502 areheated to a temperature sufficient to react the liquid chalcogen 506with the chalcogenides 502 to form a dense film of a groupIB-IIIA-chalcogenide compound 508 as shown in FIG. 1C. The dense film ofgroup IB-IIIA-chalcogenide compound is then cooled down.

Although not limited to the following, the chalcogenide particles 502may be obtained starting from a binary chalcogenide feedstock material,e.g., micron size particles or larger. Examples of chalcogenidematerials available commercially are listed below in Table I.

TABLE I Chemical Formula Typical % Purity Aluminum selenide Al2Se3 99.5Aluminum sulfide Al2S3 98 Aluminum sulfide Al2S3 99.9 Aluminum tellurideAl2Te3 99.5 Copper selenide Cu-Se 99.5 Copper selenide Cu2Se 99.5Gallium selenide Ga2Se3 99.999 Copper sulfide Cu2S (may be Cu1.8-2S)99.5 Copper sulfide CuS 99.5 Copper sulfide CuS 99.99 Copper tellurideCuTe (generally Cu1.4Te) 99.5 Copper telluride Cu2Te 99.5 Galliumsulfide Ga2S3 99.95 Gallium sulfide GaS 99.95 Gallium telluride GaTe99.999 Gallium telluride Ga2Te3 99.999 Indium selenide In2Se3 99.999Indium selenide In2Se3 99.99% Indium selenide In2Se3 99.9 Indiumselenide In2Se3 99.9 Indium sulfide InS 99.999 Indium sulfide In2S399.99 Indium telluride In2Te3 99.999 Indium telluride In2Te3 99.999

Examples of chalcogen powders and other feedstocks commerciallyavailable are listed in Table II below.

TABLE II Chemical Formula Typical % Purity Selenium metal Se 99.99Selenium metal Se 99.6 Selenium metal Se 99.6 Selenium metal Se 99.999Selenium metal Se 99.999 Sulfur S 99.999 Tellurium metal Te 99.95Tellurium metal Te 99.5 Tellurium metal Te 99.5 Tellurium metal Te99.9999 Tellurium metal Te 99.99 Tellurium metal Te 99.999 Telluriummetal Te 99.999 Tellurium metal Te 99.95 Tellurium metal Te 99.5Printing A Layer of the Extra Source of Chalcogen

Referring now to FIGS. 9A-9E, another embodiment of the presentinvention using microflakes will now be described. FIG. 9A shows asubstrate 602 with a contact layer 604 on which a microflake precursorlayer 606 is formed. An extra source of chalcogen may be provided as adiscrete layer 608 containing an extra source of chalcogen such as, butnot limited to, elemental chalcogen particles 607 over a microflakeprecursor layer 606. By way of example, and without loss of generality,the chalcogen particles may be particles of selenium, sulfur ortellurium. As shown in FIG. 9B, heat 609 is applied to the microflakeprecursor layer 606 and the layer 608 containing the chalcogen particlesto heat them to a temperature sufficient to melt the chalcogen particles607 and to react the chalcogen particles 607 with the elements in theprecursor layer 606. It should be understood that the microflakes may bemade of a variety of materials include but not limited to group IBelements, group IIIA elements, and/or group VIA elements. The reactionof the chalcogen particles 607 with the elements of the precursor layer606 forms a compound film 610 of a group IB-IIIA-chalcogenide compoundas shown in FIG. 9C. Preferably, the group IB-IIIA-chalcogenide compoundis of the form CuIn_(1-x)Ga_(x)Se_(2(1-y))S_(2y), where 0≦x≦1 and 0≦y≦1.It should be understood that in some embodiments, the precursor layer106 may be heated prior to application of the layer 108 with the extrasource of chalcogen. In other embodiments, the precursor layer 106 isnot pre-heated and the layers 106 and 108 are heated together.

In one embodiment of the present invention, the precursor layer 606 maybe between about 4.0 to about 0.5 microns thick. The layer 608containing chalcogen particles 607 may have a thickness in the range ofabout 4.0 microns to about 0.5 microns. The chalcogen particles 607 inthe layer 608 may be between about 1 nanometer and about 25 microns insize, preferably between about 25 nanometers and about 300 nanometers insize. It is noted that the chalcogen particles 607 may be initiallylarger than the final thickness of the IB-IIIA-VIA compound film 610.The chalcogen particles 607 may be mixed with solvents, carriers,dispersants etc. to prepare an ink or a paste that is suitable for wetdeposition over the precursor layer 606 to form the layer 608.Alternatively, the chalcogen particles 607 may be prepared fordeposition on a substrate through dry processes to form the layer 608.It is also noted that the heating of the layer 608 containing chalcogenparticles 607 may be carried out by an RTA process, e.g., as describedabove.

The chalcogen particles 607 (e.g., Se or S) may be formed in severaldifferent ways. For example, Se or S particles may be formed startingwith a commercially available fine mesh powder (e.g., 200 mesh/75micron) and ball milling the powder to a desirable size. A typical ballmilling procedure may use a ceramic milling jar filled with grindingceramic balls and a feedstock material, which may be in the form of apowder, in a liquid medium. When the jar is rotated or shaken, the ballsshake and grind the powder in the liquid medium to reduce the size ofthe particles of the feedstock material. Optionally, the process mayinclude dry (pre-) grinding of bigger pieces of material such as but notlimited to Se. The dry-grinding may use pieces 2-6 mm and smaller, butit would be able to handle bigger pieces as well. Note that this is truefor all size reductions where the process may start with biggerfeedstock materials, dry grinding, and subsequently starting wetgrinding (such as but not limited to ball milling). The mill itself mayrange from a small media mill to a horizontal rotating ceramic jar.

Referring now to FIG. 9D, it should also be understood that in someembodiments, the layer 608 of chalcogen particles may be formed belowthe precursor layer 606. This position of the layer 608 still allows thechalcogen particles to provide a sufficient surplus of chalcogen to theprecursor layer 606 to fully react with the group IB and group IIIAelements in layer 606. Additionally, since the chalcogen released fromthe layer 608 may be rising through the layer 606, this position of thelayer 608 below layer 606 may be beneficial to generate greaterintermixing between elements. The thickness of the layer 608 may be inthe range of about 4.0 microns to about 0.5 microns. In still otherembodiments, the thickness of layer 608 may be in the range of about 500nm to about 50 nm. In one nonlimiting example, a separate Se layer ofabout 100 nm or more might be sufficient. The coating of chalcogen mayincorporate coating with powder, Se evaporation, or other Se depositionmethod such as but not limited to chemical vapor deposition (CVD),physical vapor deposition (PVD), atomic layer deposition (ALD),electroplating, and/or similar or related methods using singly or incombination. Other types of material deposition technology may be usedto get Se layers thinner than 0.5 microns or thinner than 1.0 micron. Itshould also be understood that in some embodiments, the extra source ofchalcogen is not limited to only elemental chalcogen, but in someembodiments, may be an alloy and/or solution of one or more chalcogens.

Optionally, it should be understood that the extra source of chalcogenmay be mixed with and/or deposited within the precursor layer, insteadof as a discrete layer. In one embodiment of the present invention,oxygen-free particles or substantially oxygen-free particles ofchalcogen could be used. If the chalcogen is used with microflakesand/or plate shaped precursor materials, densification might not end upan issue due to the higher density achieved by using planar particles,so there is no reason to exclude printing Se and/or other source ofchalcogen within the precursor layer as opposed to a discrete layer.This may involve not having to heat the precursor layer to the previousprocessing temperatures. In some embodiments, this may involve formingthe film without heating above 400° C. In some embodiments, this mayinvolve not having to heat above about 300° C.

In still other embodiments of the present invention, multiple layers ofmaterial may be printed and reacted with chalcogen before deposition ofthe next layer. One nonlimiting example would be to deposit a Cu—In—Galayer, anneal it, then deposit an Se layer then treat that with RTA,follow that up by depositing another precursor layer rich in Ga,followed by another deposition of Se, and finished by a second RTAtreatment. More generically, this may include forming a precursor layer(either heat or not) then coating a layer of the extra source ofchalcogen (then heat or not) then form another layer of more precursor(heat or not) and then for another layer of the extra source ofchalcogen (then heat or not) and repeat as many times as desired tograde the composition or nucleating desired crystal sizes. In onenonlimiting example, this may be used to grade the galliumconcentration. In another embodiment, this may be used to grade thecopper concentration. In yet another embodiment, this may be used tograde the indium concentration. In a still further embodiment, this maybe used to grade the selenium concentration. In yet another embodimentthis may be used to grade the selenium concentration. Another reasonwould be to first grow copper rich films to get big crystals and then tostart adding copper-poor layers to get the stoichiometry back. Of coursethis embodiment can combined to allow the chalcogen to be deposited inthe precursor layer for any of the steps involved.

Referring now to FIG. 9E, an alternative way to take advantage of thelow melting points of chalcogens such as but not limited to Se and S isto form core-shell microflakes in which the core is a microflake 607 andthe shell 620 is a chalcogen coating. The chalcogen 620 melts andquickly reacts with the material of the core microflakes 607. As anonlimiting example, the core may be a mix of elemental particles ofgroups IB (e.g., Cu) and/or IIIA (e.g., Ga and In), which may beobtained by ball milling of elemental feedstock to a desired size.Examples of elemental feedstock materials available are listed in TableIII below. The core may also be a chalcogenide core or other material asdescribed herein.

TABLE III Chemical Formula Typical % Purity Copper metal Cu 99.99 Coppermetal Cu 99 Copper metal Cu 99.5 Copper metal Cu 99.5 Copper metal Cu 99Copper metal Cu 99.999 Copper metal Cu 99.999 Copper metal Cu 99.9Copper metal Cu 99.5 Copper metal Cu 99.9 (O₂ typ. 2-10%) Copper metalCu 99.99 Copper metal Cu 99.997 Copper metal Cu 99.99 Gallium metal Ga99.999999 Gallium metal Ga 99.99999 Gallium metal Ga 99.99 Gallium metalGa 99.9999 Gallium metal Ga 99.999 Indium metal In 99.9999 Indium metalIn 99.999 Indium metal In 99.999 Indium metal In 99.99 Indium metal In99.999 Indium metal In 99.99 Indium metal In 99.99Chalcogen-rich Chalcogenide Particles

Referring now to FIGS. 10A-10C, it should be understood that yet anotherembodiment of the present invention includes embodiments where themicroflake particles may be chalcogenide particles that arechalcogen-rich (whether they be group IB-chalcogenides, group IIIAchalcogenides, or other chalcogenides). In these embodiments, the use ofa separate source of chalcogen may not be needed since the excesschalcogen is contained within the chalcogenide particles themselves. Inone nonlimiting example of a group IB-chalcogenide, the chalcogenide maybe copper selenide, wherein the material comprises Cu_(x)Se_(y), whereinx≦y. Thus, this is a chalcogen-rich chalcogenide that will provideexcess amounts of selenium when the particles of the precursor materialare processed.

The purpose of providing an extra source of chalcogen is to first createliquid to enlarge the contact area between the initial solid particles(flakes) and the liquid. Secondly, when working with chalcogen-poorfilms, the extra source adds chalcogen to get to the stoichiometricdesired chalcogen amount. Third, chalcogens such as Se are volatile andinevitably some is lost during processing. So, main purpose is to createliquid. There are also a variety of other routes to increase the amountof liquid when the precursor layer is processed. These routes includebut are not limited to: 1) Cu—Se more Se-rich than Cu2-xSe (>377° C.,even more liquid above >523° C.); 2) Cu—Se equal to or more Se-rich thanCu2Se when adding additional Se (>220° C.); 3) In—Se of compositionIn4Se3, or in between In4Se3 and In1Se1 (>550° C.); 4) In—Se equal to ormore Se-rich than In4Se3 when adding additional Se (>220° C.); 5) In—Sein between In and In4Se3 (>156° C., preferably in an oxygen-freeenvironment since In is created 6) Ga-emulsion (>29° C., preferablyoxygen-free); and hardly (but possible) for Ga—Se. Even when workingwith Se vapor, it still would be tremendously advantageous to createadditional liquid in the precursor layer itself using one of the abovemethods or by a comparable method.

Referring now to FIG. 10A, it should be understood that the ink maycontain multiple types of particles. In FIG. 10A, the particles 704 area first type of particle and the particles 706 are a second type ofparticle. In one nonlimiting example, the ink may have multiple types ofparticles wherein only one type of particle is a chalcogenide and isalso chalcogen-rich. In other embodiments, the ink may have particleswherein at least two types of chalcogenides in the ink arechalcogen-rich. As a nonlimiting example, the ink may have Cu_(x)Se_(y)(wherein x<y) and In_(a)Se_(b) (wherein a<b). In still furtherembodiments, the ink may have particles 704, 706, and 708 (shown inphantom) wherein at least three types of chalcogenide particles are inthe ink. By way of nonlimiting example, the chalcogen-rich chalcogenideparticles may be Cu—Se, In—Se, and/or Ga—Se. All three may bechalcogen-rich. A variety of combinations are possible to obtain thedesired excess amount of chalcogen. If the ink has three types ofparticles, it should be understood that not all of the particles need tobe chalcogenides or chalcogen rich. Even within an ink with only onetype of particle, e.g. Cu—Se, there may be a mixture of chalcogen-richparticles e.g. Cu_(x)Se_(y) with x<y, and non-chalcogen-rich particles,e.g. Cu_(x)Se_(y) with x>y. As a nonlimiting example, a mixture maycontain particles of copper selenide that may have the followingcompositions: Cu₁Se₁ and Cu₁Se₂.

Referring still to FIG. 10A, it should also be understood that even withthe chalcogen-rich particles, an additional layer 710 (shown in phantom)may be also printed or coated on to the ink to provide an excess sourceof chalcogen as described previously. The material in this layer may bea pure chalcogen, a chalcogenide, or a compound that contains chalcogen.As seen in FIG. 10C, the additional layer 710 (shown in phantom) mayalso be printed onto the resulting film if further processing withchalcogen is desired.

Referring now to FIG. 10B, heat may be applied to the particles 704 and706 to begin converting them. Due to the various melting temperatures ofthe materials in the particles, some may start to assume a liquid formsooner than others. In the present invention, this is particularlyadvantageous if the materials assuming liquid form also release theexcess chalcogen as a liquid 712 which may surround the other materialsand/or elements such as 714 and 716 in the layer. FIG. 10B includes aview with an enlarged view of the liquid 712 and materials and/orelements 714 and 716.

The amount of extra chalcogen provided by all of the particles overallis at a level that is equal to or above the stoichiometric level foundin the compound after processing. In one embodiment of the presentinvention, the excess amount of chalcogen comprises an amount greaterthan the sum of 1) a stoichiometric amount found in the finalIB-IIIA-chalcogenide film and 2) a minimum amount of chalcogen necessaryto account for losses during processing to form the finalIB-IIIA-chalcogenide having the desired stoichiometric ratio. Althoughnot limited to the following, the excess chalcogen may act as a fluxthat will liquefy at the processing temperature and promote greateratomic intermixing of particles provided by the liquefied excesschalcogen. The liquefied excess chalcogen may also ensure thatsufficient chalcogen is present to react with the group IB and IIIAelements. The excess chalcogen helps to “digest” or “solubilize” theparticles or flakes. The excess chalcogen will escape from the layerbefore the desired film is fully formed.

Referring now to FIG. 10C, heat may continue to be applied until thegroup IB-IIIA chalcogenide film 720 is formed. Another layer 722 (shownin phantom) may be applied for further processing of the film 720 ifparticular features are desired. As a nonlimiting example, an extrasource of gallium may be added to the top layer and further reacted withthe film 720. Others sources may provide additional selenium to improveselenization at the top surface of the film 720. Selenization may alsooccur by using a selenium vapor atmosphere.

It should be understood that a variety of chalcogenide particles mayalso be combined with non-chalcogenide particles to arrive at thedesired excess supply of chalcogen in the precursor layer. The followingtable (Table IV) provides a non-limiting matrix of some of the possiblecombinations between chalcogenide particles listed in the rows and thenon-chalcogenide particles listed in the columns. It should also beunderstood that two more materials from the columns may be combined. Asa nonlimiting example, Cu—Ga+In+Se may also be combined even though theare from different columns. Another possibility involves, Cu—Ga+In—Ga+Se(or some other chalcogen source).

TABLE IV Cu In Ga Cu—In Se Se + Cu Se + In Se + Ga Se + Cu—In Cu—SeCu—Se + Cu Cu—Se + In Cu—Se + Ga Cu—Se + Cu—In In—Se In—Se + Cu In—Se +In In—Se + Ga In—Se + Cu—In Ga—Se Ga—Se + Ga—Se + In Ga—Se + Ga—Se + CuGa Cu—In Cu—In—Se Cu—In—Se + Cu—In—Se + Cu—In—Se + Cu—In—Se + Cu In GaCu—In Cu—Ga—Se Cu—Ga—Se + Cu—Ga—Se + Cu—Ga—Se + Cu—Ga—Se + Cu In GaCu—In In—Ga—Se In—Ga—Se + In—Ga—Se + In—Ga—Se + In—Ga—Se + Cu In Ga CuInCu—In—Ga—Se Cu—In—Ga—Se + Cu—In—Ga—Se + Cu—In—Ga—Se + Cu—In—Ga—Se + CuIn Ga CuIn Cu—Ga In—Ga Cu—In—Ga Se Se + Cu—Ga Se + In—Ga Se + Cu—In—GaCu—Se Cu—Se + Cu—Se + Cu—Se + Cu—Ga In—Ga Cu—In—Ga In—Se In—Se + In—Se +In—Ga In—Se + Cu—Ga Cu—In—Ga Ga—Se Ga—Se + Ga—Se + Ga—Se + Cu—Ga In—GaCu—In—Ga Cu—In—Se Cu—In—Se + Cu—In—Se + Cu—In—Se + Cu—Ga In—Ga Cu—In—GaCu—Ga—Se Cu—Ga—Se + Cu—Ga—Se + Cu—Ga—Se + Cu—Ga In—Ga Cu—In—Ga In—Ga—SeIn—Ga—Se + In—Ga—Se + In—Ga—Se + Cu—Ga In—Ga Cu—In—Ga Cu—In—Ga—SeCu—In—Ga—Se + Cu—In—Ga—Se + Cu—In—Ga—Se + Cu—Ga In—Ga Cu—In—Ga

In yet another embodiment, the present invention may combine a varietyof chalcogenide particles with other chalcogenide particles. Thefollowing table (Table V) provides a non-limiting matrix of some of thepossible combinations between chalcogenide particles listed for the rowsand chalcogenide particles listed for the columns.

TABLE V Cu—Se In—Se Ga—Se Cu—In—Se Se Se + Cu—Se Se + In—Se Se + Ga—SeSe + Cu—In—Se Cu—Se Cu—Se Cu—Se + Cu—Se + Cu—Se + In—Se Ga—Se Cu—In—SeIn—Se In—Se + In—Se In—Se + In—Se + Cu—Se Ga—Se Cu—In—Se Ga—Se Ga—Se +Ga—Se + Ga—Se Ga—Se + Cu—Se In—Se Cu—In—Se Cu—In—Se Cu—In—Se +Cu—In—Se + Cu—In—Se + Cu—In—Se Cu—Se In—Se Ga—Se Cu—Ga—Se Cu—Ga—Se +Cu—Ga—Se + Cu—Ga—Se + Cu—Ga—Se + Cu—Se In—Se Ga—Se Cu—In—Se In—Ga—SeIn—Ga—Se + In—Ga—Se + In—Ga—Se + In—Ga—Se + Cu—Se In—Se Ga—Se Cu—In—SeCu—In—Ga—Se Cu—In—Ga—Se + Cu—In—Ga—Se + Cu—In—Ga—Se + Cu—In—Ga—Se +Cu—Se In—Se Ga—Se Cu—In—Se Cu—Ga—Se In—Ga—Se Cu—In—Ga—Se Se Se +Cu—Ga—Se Se + In—Ga—Se Se + Cu—In—Ga—Se Cu—Se Cu—Se + Cu—Se + Cu—Se +Cu—Ga—Se In—Ga—Se Cu—In—Ga—Se In—Se In—Se + In—Se + In—Se + Cu—Ga—SeIn—Ga—Se Cu—In—Ga—Se Ga—Se Ga—Se + Ga—Se + Ga—Se + Cu—Ga—Se In—Ga—SeCu—In—Ga—Se Cu—In—Se Cu—In—Se + Cu—In—Se + Cu—In—Se + Cu—Ga—Se In—Ga—SeCu—In—Ga—Se Cu—Ga—Se Cu—Ga—Se Cu—Ga—Se + Cu—Ga—Se + In—Ga—Se Cu—In—Ga—SeIn—Ga—Se In—Ga—Se + In—Ga—Se In—Ga—Se + Cu—Ga—Se Cu—In—Ga—Se Cu—In—Ga—SeCu—In—Ga—Se + Cu—In—Ga—Se + Cu—In—Ga—Se Cu—Ga—Se In—Ga—SeNucleation Layer

Referring now to FIGS. 11A-11C, yet another embodiment of the presentinvention using particles or flakes such as but not limited tomicroflakes will now be described. This embodiment provides a method forimproving crystal growth on the substrate by depositing a thin groupIB-IIIA chalcogenide layer on the substrate to serve as a nucleationplane for film growth for the precursor layer which is formed on top ofthe thin group IB-IIIA chalcogenide layer. This nucleation layer of agroup IB-IIIA chalcogenide may be deposited, coated, or formed prior toforming the precursor layer. The nucleation layer may be formed usingvacuum or non-vacuum techniques. The precursor layer formed on top ofthe nucleation layer may be formed by a variety of techniques includingbut not limited to using an ink containing a plurality of microflakes asdescribed in this application.

FIG. 11A shows that the absorber layer may be formed on a substrate 812,as shown in FIG. 11A. A surface of the substrate 812, may be coated witha contact layer 814 to promote electrical contact between the substrate812 and the absorber layer that is to be formed on it. By way ofexample, an aluminum substrate 812 may be coated with a contact layer814 of molybdenum. As discussed herein, forming or disposing a materialor layer of material on the substrate 812 includes disposing or formingsuch material or layer on the contact layer 814, if one is used.

As shown in FIG. 11B, a nucleation layer 816 is formed on the substrate812. This nucleation layer may comprise of a group IB-IIIA chalcogenideand may be deposited, coated, or formed prior to forming the precursorlayer. As a nonlimiting example, this may be a CIGS layer, a Ga—Selayer, any other high-melting IB-IIIA-chalcogenide layer, or even a thinlayer of gallium.

Referring now to FIG. 11C, once the nucleation layer is formed, theprecursor layer 818 may be formed on top of the nucleation layer. Insome embodiments, the nucleation layer and the precursor layer may beformed simultaneously. The precursor layer 818 may contain one or moregroup IB elements and one or more group IIIA elements. Preferably, theone or more group IB elements include copper. The one or more group IIIAelements may include indium and/or gallium. The precursor layer may beformed from a film, e.g., using any of the techniques described above.

Referring still to FIG. 11C, it should also be understood that thestructure of the alternating nucleation layer and precursor layer may berepeated in the stack. FIG. 11C show that, optionally, anothernucleation layer 820 (shown in phantom) may be formed over the precursorlayer 818 to continue the structure of alternating nucleation layer andprecursor layer. Another precursor layer 822 may then be formed over thenucleation layer 820 to continue the layering, which may be repeated asdesired. Although not limited to the following, there may be 2, 3, 4, 5,6, 7, 8, 9, 10, or more sets of alternating nucleation layers andprecursor layers to build up the desired qualities. The each set mayhave different materials or amounts of materials as compared to othersets in the stack. The alternating layers may be solution deposited,vacuum deposited or the like. Different layers may be deposited bydifferent techniques. In one embodiment, this may involve solutiondepositing (or vacuum depositing) a precursor layer (optionally with adesired Cu-to-In-to-Ga ratio), subsequently adding chalcogen(solution-based, vacuum-based, or otherwise such as but not limited tovapor or H₂Se, ec . . . ), optionally heat treating this stack (duringor after introduction of the chalcogen source), subsequently depositingan additional precursor layer (optionally with a desired Cu-to-In-to-Garatio), and finally heat treating the final stack (during or after theintroduction of additional chalcogen). The goal is to create planarnucleation so that there are no holes or areas where the substrate willnot be covered by subsequent film formation and/or crystal growth.Optionally, the chalcogen source may also be introduced before addingthe first precursor layer containing Cu+In+Ga. It should also beunderstood that in some other embodiments, layer 820 may be a chalcogencontaining layer, such as but not limited to a selenium layer, and beheated with each precursor layer (or at the end after all precursorlayers are formed).

Nucleation Layer by Thermal Gradient

Referring now to FIGS. 12A-12B, it should be understood that anucleation layer for use with a microflake based precursor material mayalso be formed by creating a thermal gradient in the precursor layer850. As a nonlimiting example, the nucleation layer 852 may be formedstarting from the upper portion of the precursor layer or optionally byforming the nucleation layer 854 from a lower portion of the precursorlayer. In one embodiment of the present invention, the nucleation layermay be viewed as being a layer where an initial IB-IIIA-VIA compoundcrystal growth is preferred over crystal growth in another location ofthe precursor layer and/or stacks of precursor layers. The nucleationlayer 852 or 854 is formed by creating a thermal gradient in theprecursor layer such that one portion of the layer reaches a temperaturesufficient to begin crystal growth. The nucleation layer may be in theform a nucleation plane having a substantially planar configuration topromote a more even crystal growth across the substrate while minimizingthe formation of pinholes and other anomalies.

As seen in FIG. 12A, in one embodiment of the present invention, thethermal gradient used to form the nucleation layer 852 may be created byusing a laser 856 to increase only an upper portion of the precursorlayer 850 to a processing temperature. The laser 856 may be pulsed orotherwise controlled to not heat the entire thickness of the precursorlayer to a processing temperature. The backside 858 of the precursorlayer and the substrate 860 supporting it may be in contact with cooledrollers 862, cooled planar contact surface, or cooled drums whichprovide an external source of cooling to prevent lower portions of thelayer from reaching processing temperature. Cooled gas 864 may also beprovided on one side of the substrate and adjacent portion of theprecursor layer to lower the temperature of the precursor layer below aprocessing temperature where nucleation to the finalIB-IIIA-chalcogenide compound begins. It should be understood that otherdevices may be used to heat the upper portion of the precursor layersuch as but not limited to, pulsed thermal processing, plasma heating,or heating via IR lamps.

As seen in FIG. 12B, in another embodiment of the present invention, thenucleation layer 854 may be formed on a lower portion of the precursorlayer 850 using techniques similar to those described above. Since thesubstrate 860 used with the present invention may be selected to bethermally conductive, underside heating of the substrate will also causeheating of a lower portion of the precursor layer. The nucleation planewill then form along the bottom portion of the lower portion. The upperportion of the precursor layer may be cooled by a variety of techniquessuch as, but not limited to, cooled gas, cooled rollers, or othercooling device.

After the nucleation layer has formed, preferably consisting of materialidentical or close to the final IB-IIIA-chalcogenide compound, theentire precursor layer, or optionally only those portions of theprecursor layer that remain more or less unprocessed, will be heated tothe processing temperature so that the remaining material will begin toconvert into the final IB-IIIA-chalcogenide compound in contact with thenucleation layer. The nucleation layer guides the crystal formation andminimizes the possibility of areas of the substrate forming pinhole orhaving other abnormalities due to uneven crystal formation.

It should be understood that in addition to the aforementioned, thetemperature may also vary over different time periods of precursor layerprocessing. As a nonlimiting example, the heating may occur at a firsttemperature over an initial processing time period and proceed to othertemperatures for subsequent time periods of the processing. Optionally,the method may include intentionally creating one or more temperaturedips so that, as a nonlimiting example, the method comprises heating,cooling, heating, and subsequent cooling. In one embodiment of thepresent invention, this may involve lowering the temperature frombetween about 50° C. to about 200° C. from a temperature in an initialtime period.

Nucleation Layer by Chemical Gradient

Referring now to FIGS. 13A-13F, a still further method of forming anucleation layer with a microflake precursor material according to thepresent invention will be described in more detail. In this embodimentof the present invention, the composition of the deposited layers ofprecursor material may be selected so that crystal formation beginssooner in some layers than in other layers. It should be understood thatthe various methods of forming a nucleation layer may be combinedtogether to facilitate layer formation. As a nonlimiting example, thethermal gradient and chemical gradient methods may be combined tofacilitate nucleation layer formation. It is imagined that single ormultiple combinations of using a thermal gradient, chemical gradient,and/or thin film nucleation layer may be combined.

Referring now to FIG. 13A, the absorber layer may be formed on asubstrate 912, as shown in FIG. 13A. A surface of the substrate 912 maybe coated with a contact layer 914 to promote electrical contact betweenthe substrate 912 and the absorber layer that is to be formed on it. Byway of example, an aluminum substrate 912 may be coated with a contactlayer 914 of molybdenum. As discussed herein, forming or disposing amaterial or layer of material on the substrate 912 includes disposing orforming such material or layer on the contact layer 914, if one is used.Optionally, it should also be understood that a layer 915 may also beformed on top of contact layer 914 and/or directly on substrate 912.This layer may be solution coated, evaporated, and/or deposited usingvacuum based techniques. Although not limited to the following, thelayer 915 may have a thickness less than that of the precursor layer916. In one nonlimiting example, the layer may be between about 1 toabout 100 nm in thickness. The layer 915 may be comprised of variousmaterials including but not limited to at least one of the following: agroup IB element, a group IIIA element, a group VIA element, a group IAelement (new style: group 1), a binary and/or multinary alloy of any ofthe preceding elements, a solid solution of any of the precedingelements, copper, indium, gallium, selenium, copper indium, coppergallium, indium gallium, sodium, a sodium compound, sodium fluoride,sodium indium sulfide, copper selenide, copper sulfide, indium selenide,indium sulfide, gallium selenide, gallium sulfide, copper indiumselenide, copper indium sulfide, copper gallium selenide, copper galliumsulfide, indium gallium selenide, indium gallium sulfide, copper indiumgallium selenide, and/or copper indium gallium sulfide.

As shown in FIG. 13B, a precursor layer 916 is formed on the substrate.The precursor layer 916 contains one or more group IB elements and oneor more group IIIA elements. Preferably, the one or more group IBelements include copper. The one or more group IIIA elements may includeindium and/or gallium. The precursor layer may be formed using any ofthe techniques described above. In one embodiment, the precursor layercontains no oxygen other than those unavoidably present as impurities orincidentally present in components of the film other than themicroflakes themselves. Although the precursor layer 916 is preferablyformed using non-vacuum methods, it should be understood that it mayoptionally be formed by other means, such as evaporation, sputtering,ALD, etc. By way of example, the precursor layer 916 may be anoxygen-free compound containing copper, indium and gallium. In oneembodiment, the non-vacuum system operates at pressures above about 3.2kPa (24 Torr). Optionally, it should also be understood that a layer 917may also be formed on top of precursor layer 916. It should beunderstood that the stack may have both layers 915 and 917, only one ofthe layers, or none of the layers. Although not limited to thefollowing, the layer 917 may have a thickness less than that of theprecursor layer 916. In one nonlimiting example, the layer may bebetween about 1 to about 100 nm in thickness. The layer 917 may becomprised of various materials including but not limited to at least oneof the following: a group IB element, a group IIIA element, a group VIAelement, a group IA element (new style: group 1), a binary and/ormultinary alloy of any of the preceding elements, a solid solution ofany of the preceding elements, copper, indium, gallium, selenium, copperindium, copper gallium, indium gallium, sodium, a sodium compound,sodium fluoride, sodium indium sulfide, copper selenide, copper sulfide,indium selenide, indium sulfide, gallium selenide, gallium sulfide,copper indium selenide, copper indium sulfide, copper gallium selenide,copper gallium sulfide, indium gallium selenide, indium gallium sulfide,copper indium gallium selenide, and/or copper indium gallium sulfide.

Referring now to FIG. 13C, a second precursor layer 918 of a secondprecursor material may optionally be applied on top of the firstprecursor layer. The second precursor material may have an overallcomposition that is more chalcogen-rich than the first precursormaterial in precursor layer 916. As a nonlimiting example, this allowsfor creating a gradient of available Se by doing two coatings(preferably with only one heating process of the stack after depositingboth precursor layer coatings) where the first coating containsselenides with relatively less selenium in it (but still enough) thanthe second. For instance, the precursor for the first coating cancontain Cu_(x)Se_(y) where the x is larger than in the second coating.Or it may contain a mix of Cu_(x)Se_(y) particles wherein there is alarger concentration (by weight) of the selenide particles with thelarge x. In this current embodiment, each layer has preferably thetargeted stoichiometry because the C/I/G ratios are kept the same foreach precursor layer. Again, although this second precursor layer 918 ispreferably formed using non-vacuum methods, it should be understood thatit may optionally be formed by other means, such as evaporation,sputtering, ALD, etc.

The rationale behind the use of chalcogen grading, or more general agrading in melting temperature from bottom to top, is to control therelative rate of crystallization in depth and to have thecrystallization happen e.g. faster at the bottom portion of the stack ofprecursor layers than at the top of the stack of precursor layers. Theadditional rationale is that the common grain structure in typicalefficient solution-deposited CIGS cells where the cells have largegrains at the top of the photoactive film, which is the part of thephotoactive film that is mainly photoactive, and small grains at theback, still have appreciable power conversion efficiencies. It should beunderstood that in other embodiments, a plurality of many layers ofdifferent precursor materials may be used to build up a desired gradientof chalcogen, or more general, a desired gradient in melting temperatureand/or subsequent solidification into the final IB-IIIA-chalcogenidecompound, or even more general, a desired gradient in melting and/orsubsequent solidification into the final IB-IIIA-chalcogenide compound,either due to creating a chemical (compositional) gradient, and/or athermal gradient, in the resulting film. As nonlimiting examples, thepresent invention may use particles and/or microflakes and/or nanoflakeswith different melting points such as but not limited to lower meltingmaterials Se, In₄Se₃, Ga, and Cu₁Se₁, compared to higher meltingmaterials In₂Se₃, Cu₂Se.

Referring now to FIG. 13C, heat 920 is applied to heat the firstprecursor layer 916 and the second precursor layer 918 into a groupIB-IIIA compound film 922. The heat 920 may be supplied in a rapidthermal annealing process, e.g., as described above. Specifically, thesubstrate 912 and precursor layer(s) 916 and/or 918 may be heated froman ambient temperature to a plateau temperature range of between about200° C. and about 600° C. The temperature is maintained in the plateaurange for a period of time ranging between about a fraction of a secondto about 60 minutes, and subsequently reduced.

Optionally, as shown in FIG. 13D, it should be understood that a layer924 containing elemental chalcogen particles may be applied over theprecursor layers 916 and/or 918 prior to heating. Of course, if thematerial stack does not include a second precursor layer, the layer 924is formed over the precursor layer 916. By way of example, and withoutloss of generality, the chalcogen particles may be particles ofselenium, sulfur or tellurium. Such particles may be fabricated asdescribed above. The chalcogen particles in the layer 924 may be betweenabout 1 nanometer and about 25 microns in size, preferably between 50 nmand 500 nm. The chalcogen particles may be mixed with solvents,carriers, dispersants etc. to prepare an ink or a paste that is suitablefor wet deposition over the precursor layer 916 and/or 918 to form thelayer 924. Alternatively, the chalcogen particles may be prepared fordeposition on a substrate through dry processes to form the layer 924.

Optionally, as shown in FIG. 13E, a layer 926 containing an additionalchalcogen source, and/or an atmosphere containing a chalcogen source,may optionally be applied to layer 922, particularly if layer 924 wasnot applied in FIG. 13D. Heat 928 may optionally be applied to layer 922and the layer 926 and/or atmosphere containing the chalcogen source toheat them to a temperature sufficient to melt the chalcogen source andto react the chalcogen source with the group IB element and group IIIAelements in the precursor layer 922. The heat 928 may be applied in arapid thermal annealing process, e.g., as described above. The reactionof the chalcogen source with the group IB and IIIA elements forms acompound film 930 of a group IB-IIIA-chalcogenide compound as shown inFIG. 13F. Preferably, the group IB-IIIA-chalcogenide compound is of theform Cu_(z)In_(1-x)Ga_(x)Se_(2(1-y))S_(2y), where 0≦x≦1, 0≦y≦1, and0.5≦y≦1.5.

Referring still to FIGS. 13A-13F, it should be understood that sodiummay also be used with the precursor material to improve the qualities ofthe resulting film. In a first method, as discussed in regards to FIGS.13A and 13B, one or more layers of a sodium containing material may beformed above and/or below the precursor layer 916. The formation mayoccur by solution coating and/or other techniques such as but notlimited to sputtering, evaporation, CBD, electroplating, sol-gel basedcoating, spray coating, chemical vapor deposition (CVD), physical vapordeposition (PVD), atomic layer deposition (ALD), and the like.

Optionally, in a second method, sodium may also be introduced into thestack by sodium doping the microflakes and/or particles in the precursorlayer 916. As a nonlimiting example, the microflakes and/or otherparticles in the precursor layer 916 may be a sodium containing materialsuch as, but not limited to, Cu—Na, In—Na, Ga—Na, Cu—In—Na, Cu—Ga—Na,In—Ga—Na, Na—Se, Cu—Se—Na, In—Se—Na, Ga—Se—Na, Cu—In—Se—Na, Cu—Ga—Se—Na,In—Ga—Se—Na, Cu—In—Ga—Se—Na, Na—S, Cu—S—Na, In—S—Na, Ga—S—Na,Cu—In—S—Na, Cu—Ga—S—Na, In—Ga—S—Na, and/or Cu—In—Ga—S—Na. In oneembodiment of the present invention, the amount of sodium in themicroflakes and/or other particles may be about 1 at. % or less. Inanother embodiment, the amount of sodium may be about 0.5 at. % or less.In yet another embodiment, the amount of sodium may be about 0.1 at. %or less. It should be understood that the doped particles and/or flakesmay be made by a variety of methods including milling feedstock materialwith the sodium containing material and/or elemental sodium.

Optionally, in a third method, sodium may be incorporated into the inkitself, regardless of the type of particle, nanoparticle, microflake,and/or nanoflakes dispersed in the ink. As a nonlimiting example, theink may include microflakes (Na doped or undoped) and a sodium compoundwith an organic counter-ion (such as but not limited to sodium acetate)and/or a sodium compound with an inorganic counter-ion (such as but notlimited to sodium sulfide). It should be understood that sodiumcompounds added into the ink (as a separate compound), might be presentas particles (e.g. nanoparticles), or dissolved, and/or in (reverse)micelles. The sodium may be in “aggregate” form of the sodium compound(e.g. dispersed particles), and the “molecularly dissolved” form.

Optionally, in a fourth method, sodium may be added in a separate step.This may occur before the heating step, during the heating step, orafter the heating step. In a two-step heating process, the sodium may beadded before the first heating step, during the first heating step, orafter the first heating step but prior to the second heating step whichmay be in a reactive atmosphere (such as but not limited to beingbetween densification and selenization). This deposition of sodium orsodium containing material may occur by any of the deposition methodsdisclosed herein including but not limited to spray or coating method.The sodium or sodium containing material may be any of those set forthherein.

None of the four aforementioned methods are mutually exclusive and maybe applied singly or in any single or multiple combination to providethe desired amount of sodium to the stack containing the precursormaterial. Additionally, sodium and/or a sodium containing compound mayalso be added to the substrate (e.g. into the molybdenum target). Also,sodium-containing layers may be formed in between one or more precursorlayers if multiple precursor layers (using the same or differentmaterials) are used. It should also be understood that the source of thesodium is not limited to those materials previously listed. As anonlimiting example, basically, any deprotonated alcohol where theproton is replaced by sodium, any deprotonated organic and inorganicacid, the sodium salt of the (deprotonated) acid,Na_(x)H_(y)Se_(z)S_(u)Te_(v)O_(w) where x, y, z, u, v, and w≦0,Na_(x)Cu_(y)In_(z)Ga_(u)O_(v) where x, y, z, u, and v≦0, sodiumhydroxide, sodium acetate, and the sodium salts of the following acids:butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoicacid, tetradecanoic acid, hexadecanoic acid, 9-hexadecenoic acid,octadecanoic acid, 9-octadecenoic acid, 11-octadecenoic acid,9,12-octadecadienoic acid, 9,12,15-octadecatrienoic acid, and/or6,9,12-octadecatrienoic acid.

Optionally, as seen in FIG. 13F, it should also be understood thatsodium and/or a sodium compound may be added to the processedchalcogenide film after the precursor layer has been heated or otherwiseprocessed. This embodiment of the present invention thus modifies thefilm after CIGS formation. With sodium, carrier trap levels associatedwith the grain boundaries are reduced, permitting improved electronicproperties in the film. A variety of sodium containing materials such asthose listed above may be deposited as layer 932 onto the processed filmand then annealed to treat the CIGS film.

Additionally, the sodium material may be combined with other elementsthat can provide a bandgap widening effect. Two elements which wouldachieve this include gallium and sulfur. The use of one or more of theseelements, in addition to sodium, may further improve the quality of theabsorber layer. The use of a sodium compound such as but not limited toNa₂S, NaInS₂, or the like provides both Na and S to the film and couldbe driven in with an anneal such as but not limited to an RTA step toprovide a layer with a bandgap different from the bandgap of theunmodified CIGS layer or film.

Referring now to FIG. 14, embodiments of the invention may be compatiblewith roll-to-roll manufacturing. Specifically, in a roll-to-rollmanufacturing system 1000 a flexible substrate 1001, e.g., aluminum foiltravels from a supply roll 1002 to a take-up roll 404. The width of therow may vary depending on the application. Some embodiments have aroll(s) with a width greater than 0.5 m, greater than 1.0 m, greaterthan 2.0m, and/or greater than 3.0 m or more. These substrates may behigh aspect ratio with lengths substantially greater than the width suchas but not limited to aspect ratios of 50:1, 100:1, or more. 1004. Inbetween the supply and take-up rolls, the substrate 1001 passes a numberof applicators 1006A, 1006B, 1006C, e.g. microgravure rollers and heaterunits 1008A, 1008B, 1008C. Each applicator deposits a different layer orsub-layer of a photovoltaic device active layer, e.g., as describedabove. The heater units are used to anneal the different sub-layers. Inthe example depicted in FIG. 14, applicators 1006A and 1006B may beapplied different sub-layers of a precursor layer (such as precursorlayer 106, precursor layer 916, or precursor layer 918). Heater units1008A and 1008B may anneal each sub-layer before the next sub-layer isdeposited. Alternatively, both sub-layers may be annealed at the sametime. Applicator 1006C may apply a layer of material containingchalcogen particles as described above. Heater unit 1008C heats thechalcogen layer and precursor layer as described above. Note that it isalso possible to deposit the precursor layer (or sub-layers) thendeposit the chalcogen-containing layer and then heat all three layerstogether to form the IB-IIIA-chalcogenide compound film used for thephotovoltaic absorber layer.

The total number of printing steps can be modified to construct absorberlayers with bandgaps of differential gradation. For example, additionallayers (fourth, fifth, sixth, and so forth) can be printed (andoptionally annealed between printing steps) to create an even morefinely-graded bandgap within the absorber layer. Alternatively, fewerfilms (e.g. double printing) can also be printed to create a lessfinely-graded bandgap. For any of the above embodiments, it is possibleto have different amounts of chalcogen in each layer as well to varycrystal growth that may be influenced by the amount of chalcogenpresent.

Additionally, it should be understood that any number of combinations offlake and non-flake particles may be used according to the presentinvention in the various layers. As a nonlimiting example, thecombinations may include but are not limited to:

TABLE VI Combination 1 1) chalcogenide (flake) + non-chalcogenide(flake) Combination 2 2) chalcogenide (flake) + non-chalcogenide(non-flake) Combination 3 3) chalcogenide (non-flake) + non-chalcogenide(flake) Combination 4 4) chalcogenide (non-flake) + non-chalcogenide(non-flake) Combination 5 5) chalcogenide (flake) + chalcogenide (flake)Combination 6 6) chalcogenide (flake) + chalcogenide (non-flake)Combination 7 7) chalcogenide (non-flake) + chalcogenide (non-flake)Combination 8 8) non-chalcogenide (flake) + non-chalcogenide (flake)Combination 9 9) non-chalcogenide (flake) + non-chalcogenide (non-flake)Combination 10 10) non-chalcogenide (non-flake) + non-chalcogenide(non-flake)

Although not limited to the following, the chalcogenide andnon-chalcogenide materials may be selected from any of those listed inthe Tables IV and V.

Reduced Melting Temperature

In yet another embodiment of the present invention, the ratio ofelements within a particle or flake may be varied to produce moredesired material properties. In one nonlimiting example, this embodimentcomprises using desired stoichiometric ratios of elements so that theparticles used in the ink have a reduced melting temperature. By way ofnonlimiting example, for a group IB chalcogenide, the amount of thegroup IB element and the amount of the chalcogen is controlled to movethe resulting material to a portion of the phase diagram that has areduced melting temperature. Thus for Cu_(x)Se_(y), the values for x andy are selected to create a material with reduced melting temperature asdetermined by reference to a phase diagram for the material. Phasediagrams for the following materials may be found in ASM Handbook,Volume 3 Alloy Phase Diagrams (1992) by ASM International and fullyincorporated herein by reference for all purposes. Some specificexamples may be found on pages 2-168, 2-170, 2-176, 2-178, 2-208, 2-214,2-257, and/or 2-259.

As a nonlimiting example, copper selenide has multiple meltingtemperatures depending on the ratio of copper to selenium in thematerial. Everything more Se-rich (i.e. right on the binary phasediagram with pure Cu on the left and pure Se on the right) of thesolid-solution Cu₂-xSe will create liquid selenium. Depending oncomposition, the melting temperature may be as low as 221° C. (more Serich than Cu₁Se₂), as low as 332° C. (for compositions between Cu₁Se₁ &Cu₁Se₂), and as low as 377° C. (for compositions between Cu₂-xSe andCu₁Se₁). At 523° C. and above, the material is all liquid for Cu—Se thatis more Se-rich than the eutectic (˜57.9 wt.-% Se). For compositions inbetween the solid-solution Cu₂-xSe and the eutectic (˜57.9 wt.-% Se), itwill create a solid solid-solution Cu₂-xSe and liquid eutectic (˜57.9wt.-% Se) at 523° C. and just above.

Another nonlimiting example involves gallium selenide which may havemultiple melting temperatures depending on the ratio of gallium toselenium in the material. Everything more Se-rich (i.e. right on thebinary phase diagram with pure Ga on the left and pure Se on the right)than Ga₂Se₃ will create liquid above 220° C., which is mainly pure Se.Making Ga—Se more Se-rich than Ga₁Se₁ is possible by making e.g. thecompound Ga₂Se₃ (or anything more Se-rich than Ga₁Se₁), but only whenadding other sources of selenium when working with a composition inbetween or equal to Ga₁Se₁ and Ga₂Se₃ (being an additional source ofselenium or Se-rich Cu—Se) will liquefy the Ga—Se at processingtemperature. Hence, an additional source of Se may be provided tofacilitate the creation of a liquid involving gallium selenide.

Yet another nonlimiting example involves indium selenide which may havemultiple melting temperatures depending on the ratio of indium toselenium in the material. Everything more Se-rich (i.e. right on thebinary phase diagram with pure In on the left and pure Se on the right)than In₂Se₃ will create liquid above 220° C., which is mainly pure Se.Making In—Se more Se-rich than In₁Se₁ would create liquid for In₂Se₃ andalso for In₆Se₇ (or a bulk composition in between In₁Se₁ and Se), butwhen dealing with a composition between or equal to In₁Se₁ and In₂Se₃,only by adding other sources of selenium (being an additional source ofselenium or Se-rich Cu—Se) the In—Se will liquefy at processingtemperature. Optionally for In—Se, there is another way of creating moreliquid by going in the “other” direction and using compositions that areless Se-rich (i.e. left on the binary phase diagram). By using amaterial composition between pure In and In₄Se₃ (or between In andIn₁Se₁ or between In and In6Se7 depending on temperature), pure liquidIn can be created at 156° C. and even more liquid at 520° C. (or at ahigher temperature when going more Se-rich moving from the eutecticpoint of ˜24.0 wt.-% Se up to In₁Se₁). Basically, for a bulk compositionless Se-rich than the In—Se eutectic (−24.0 wt.-% Se), all the In—Sewill turn into a liquid at 520° C. Of course, with these type of Se poormaterials, one of the other particles (such as but not limited to Cu₁Se₂and/or Se) will be needed to increase the Se content, or another sourceof Se.

Accordingly, liquid may be created at our processing temperature by: 1)adding a separate source of selenium, 2) using Cu—Se more Se-rich thanCu₂-xSe, 3) using Ga-emulsion (or In—Ga emulsion), or In (in an air freeenvironment), or 4) using In—Se less Se-rich than In1Se1 though this mayalso require an air free environment. When copper selenide is used, thecomposition may be Cu_(x)Se_(y), wherein x is in the range of about 2 toabout 1 and y is in the range of about 1 to about 2. When indiumselenide is used, the composition may be In_(x)Se_(y), wherein x is inthe range of about 1 to about 6 and y is in the range of about 0 toabout 7. When gallium selenide is used, the composition may beGa_(x)Se_(y), wherein x is in the range of about 1 to about 2 and y isin the range of about 1 to about 3.

It should be understood that adding a separate source of selenium willmake the composition behave initially as more Se-rich at the interfaceof the selenide particle and the liquid selenium at the processingtemperature.

Additional Chalcogen

Any of the methods described herein may be further optimized by using,prior to, during, or after the solution deposition and/or heating of oneor more of the precursor layers, any combination of (1) any chalcogensource that can be solution-deposited, e.g. a Se or S nano- ormicron-sized powder mixed into the precursor layers or deposited as aseparate layer, (2) chalcogen (e.g., Se or S) evaporation, (3) an H₂Se(H₂S) atmosphere, (4) a chalcogen (e.g., Se or S) atmosphere, (5) an H₂atmosphere, (6) an organo-selenium atmosphere, e.g. diethylselenide oranother organo-metallic material, (7) another reducing atmosphere, e.g.CO, and a (8) heat treatment. The stoichiometric ratio of microflakes toextra chalcogen, given as Se/(Cu+In+Ga+Se) may be in the range of about0 to about 1000.

For example as shown in FIG. 15A, a layer 1018 containing elementalchalcogen particles 1017 over the precursor layer 1016. By way ofexample, and without loss of generality, the chalcogen particles may beparticles of selenium, sulfur or tellurium. As shown in FIG. 15B, heat1019 is applied to the precursor layer 1016 and the layer 1018containing the chalcogen particles to heat them to a temperaturesufficient to melt the chalcogen particles 1017 and to react thechalcogen particles 1017 with the group IB element and group IIIAelements in the precursor layer 1016. The reaction of the chalcogenparticles 1017 with the group IB and IIIA elements forms a compound film1810 of a group IB-IIIA-chalcogenide compound as shown in FIG. 15C.Optionally, the group IB-IIIA-chalcogenide compound is of the formCu_(z)In_(1-x)Ga_(x)Se_(2(1-y))S_(y), where 0≦x≦1, 0≦y≦1, and 0.5≦z≦1.5.

If the chalcogen particles 1017 melt at a relatively low temperature(e.g., 220° C. for Se, 120° C. for S) the chalcogen is already in aliquid state and makes good contact with the group IB and IIIAnanoparticles in the precursor layer 1016. If the precursor layer 1016and molten chalcogen are then heated sufficiently (e.g., at about 375°C.) the chalcogen reacts with the group IB and IIIA elements in theprecursor layer 1016 to form the desired IB-IIIA-chalcogenide materialin the compound film 1810. As one nonlimiting example, the precursorlayer is between about 10 nm and about 5000 nm thick. In otherembodiments, the precursor layer may be between about 4.0 to about 0.5microns thick.

There are a number of different techniques for forming the IB-IIIAprecursor layer 1016. For example, the precursor layer 1016 may beformed from a nanoparticulate film including nanoparticles containingthe desired group IB and IIIA elements. The nanoparticles may be amixture elemental nanoparticles, i.e., nanoparticles having only asingle atomic species. Alternatively, the nanoparticles may be binarynanoparticles, e.g., Cu—In, In—Ga, or Cu—Ga or ternary particles, suchas, but not limited to, Cu—In—Ga, or quaternary particles. Suchnanoparticles may be obtained, e.g., by ball milling a commerciallyavailable powder of the desired elemental, binary or ternary material.These nanoparticles may be between about 0.1 nanometer and about 500nanometers in size.

One of the advantages of the use of nanoparticle-based dispersions isthat it is possible to vary the concentration of the elements within thecompound film 1810 either by building the precursor layer in a sequenceof sub-layers or by directly varying the relative concentrations in theprecursor layer 1016. The relative elemental concentration of thenanoparticles that make up the ink for each sub-layer may be varied.Thus, for example, the concentration of gallium within the absorberlayer may be varied as a function of depth within the absorber layer.

The layer 1018 containing the chalcogen particles 1017 may be disposedover the nanoparticulate film and the nanoparticulate film (or one ormore of its constituent sub-layers) may be subsequently heated inconjunction with heating the chalcogen particles 1017. Alternatively,the nanoparticulate film may be heated to form the precursor layer 1016before disposing the layer 1018 containing elemental chalcogen particles1017 over precursor layer 1016. Additional disclosure on depositingchalcogen material may be found in co-pending U.S. patent applicationSer. No. 11/361,522 filed Feb. 23, 2006 and fully incorporated herein byreference for all purposes.

Referring now to FIG. 15E, yet another embodiment of the presentinvention will now be described. In this embodiment for use with amicroflake precursor material, it should be understood that overpressurefrom chalcogen vapor is used to provide a chalcogen atmosphere toimprove processing of the film and crystal growth. FIG. 15E shows achamber 1050 with a substrate 1052 having a contact layer 1054 and aprecursor layer 1056. Extra sources 1058 of chalcogen are included inthe chamber and are brought to a temperature to generate chalcogen vaporas indicated by lines 1060. In one embodiment of the present invention,the chalcogen vapor is provided to have a partial pressure of thechalcogen present in the atmosphere greater than or equal to the vaporpressure of chalcogen that would be required to maintain a partialchalcogen pressure at the processing temperature and processing pressureto minimize loss of chalcogen from the precursor layer, and if desired,provide the precursor layer with additional chalcogen. The partialpressure is determined in part on the temperature that the chamber 1050or the precursor layer 1056 is at. It should also be understood that thechalcogen vapor is used in the chamber 1050 at a non-vacuum pressure. Inone embodiment, the pressure in the chamber is at about atmosphericpressure. Per the ideal gas law PV=nRT, it should be understood that thetemperature influences the vapor pressure. In one embodiment, thischalcogen vapor may be provided by using a partially or fully enclosedchamber with a chalcogen source 1062 therein or coupled to the chamber.In another embodiment using a more open chamber, the chalcogenatmosphere may be provided by supplying a source producing a chalcogenvapor. The chalcogen vapor may serve to help keep the chalcogen in thefilm or to provide the chalcogen to covert the precursor layer. Thus,the chalcogen vapor may or may not be used to provide excess chalcogen.In some embodiments, this may serve more to keep the chalcogen presentin the film than to provide more chalcogen into the film. Optionally,this vapor or atmosphere maybe used as a chalcogen that is introducedinto an otherwise chalcogen free or selenium free precursor layer. Itshould be understood that theThe exposure to chalcogen vapor may occurin a non-vacuum environment. The exposure to chalcogen vapor may occurat or near atmospheric pressure. These conditions may be applicable toany of the embodiments described herein. The chalcogen may be carriedinto the chamber by a carrier gas. The carrier gas may be an inert gassuch as nitrogen, argon, or the like. This chalcogen atmosphere systemmay be adapted for use in a roll-to-roll system.

Referring now to FIG. 15F, it shown that the present invention may beadopted for use with a roll-to-roll system where the substrate 1070carrying the precursor layer may be flexible and configured as rolls1072 and 1074. The chamber 1076 may be at vacuum or non-vacuumpressures. The chamber 1076 may be designed to incorporate adifferential valve design to minimize the loss of chalcogen vapor at thechamber entry and chamber exit points of the roll-to-roll substrate1070.

Referring now to FIG. 15G, yet another embodiment of the presentinvention uses a chamber 1090 of sufficient size to hold the entiresubstrate, including any rolls 1072 or 1074 associated with using aroll-to-roll configuration.

Referring now to FIG. 16A, it should also be understood that theembodiments of the present invention may also be used on a rigidsubstrate 1100. By way of nonlimiting example, the rigid substrate 1100may be glass, soda-lime glass, steel, stainless steel, aluminum,polymer, ceramic, coated polymer, or other rigid material suitable foruse as a solar cell or solar module substrate. A high speedpick-and-place robot 1102 may be used to move rigid substrates 1100 ontoa processing area from a stack or other storage area. In FIG. 16A, thesubstrates 1100 are placed on a conveyor belt which then moves themthrough the various processing chambers. Optionally, the substrates 1100may have already undergone some processing by the time and may alreadyinclude a precursor layer on the substrate 1100. Other embodiments ofthe invention may form the precursor layer as the substrate 1100 passesthrough the chamber 1106.

FIG. 16B shows another embodiment of the present system where apick-and-place robot 1110 is used to position a plurality of rigidsubstrates on a carrier device 1112 which may then be moved to aprocessing area as indicated by arrow 1114. This allows for multiplesubstrates 1100 to be loaded before they are all moved together toundergo processing.

Referring now to FIG. 17, yet another embodiment of the presentinvention will now be described. In one embodiment, the particles usedto form a precursor layer 1500 may include particles that areinter-metallic particles 1502. In one embodiment, an inter-metallicmaterial is a material containing at least two elements, wherein theamount of one element in the inter-metallic material is less than about50 molar percent of the total molar amount of the inter-metallicmaterial and/or the total molar amount of that one element in aprecursor material. The amount of the second element is variable and mayrange from less than about 50 molar percent to about 50 or more molarpercent of the inter-metallic material and/or the total molar amount ofthat one element in a precursor material. Alternatively, inter-metallicphase materials may be comprised of two or more metals where thematerials are admixed in a ratio between the upper bound of the terminalsolid solution and an alloy comprised of about 50% of one of theelements in the inter-metallic material. The particle distribution shownin the enlarged view of FIG. 17 is purely exemplary and is nonlimiting.It should be understood that some embodiments may have particles thatall contain inter-metallic materials, mixture of metallic andinter-metallic materials, metallic particles and inter-metallicparticles, or combinations thereof.

It should be understood that inter-metallic phase materials arecompounds and/or intermediate solid solutions containing two or moremetals, which have characteristic properties and crystal structuresdifferent from those of either the pure metals or the terminal solidsolutions. Inter-metallic phase materials arise from the diffusion ofone material into another via crystal lattice vacancies made availableby defects, contamination, impurities, grain boundaries, and mechanicalstress. Upon two or more metals diffusing into one another, intermediatemetallic species are created that are combinations of the two materials.Sub-types of inter-metallic compounds include both electron andinterstitial compounds.

Electron compounds arise if two or more mixed metals are of differentcrystal structure, valency, or electropositivity relative to oneanother; examples include but are not limited to copper selenide,gallium selenide, indium selenide, copper telluride, gallium telluride,indium telluride, and similar and/or related materials and/or blends ormixtures of these materials.

Interstitial compounds arise from the admixture of metals or metals andnon-metallic elements, with atomic sizes that are similar enough toallow the formation of interstitial crystal structures, where the atomsof one material fit into the spaces between the atoms of anothermaterial. For inter-metallic materials where each material is of asingle crystal phase, two materials typically exhibit two diffractionpeaks, each representative of each individual material, superimposedonto the same spectra. Thus inter-metallic compounds typically containthe crystal structures of both materials contained within the samevolume. Examples include but are not limited to Cu—Ga, Cu—In, andsimilar and/or related materials and/or blends or mixtures of thesematerials, where the compositional ratio of each element to the otherplaces that material in a region of its phase diagram other than that ofthe terminal solid solution.

Inter-metallic materials are useful in the formation of precursormaterials for CIGS photovoltaic devices in that metals interspersed in ahighly homogenous and uniform manner amongst one another, and where eachmaterial is present in a substantially similar amount relative to theother, thus allowing for rapid reaction kinetics leading to high qualityabsorber films that are substantially uniform in all three dimensionsand at the nano-, micro, and meso-scales.

In the absence of the addition of indium nanoparticles, which aredifficult to synthesize and handle, terminal solid solutions do notreadily allow a sufficiently large range of precursor materials to beincorporated into a precursor film in the correct ratio (e.g.Cu/(In+Ga)=0.85) to provide for the formation of a highly lightabsorbing, photoactive absorber layer. Furthermore, terminal solidsolutions may have mechanical properties that differ from those ofinter-metallic materials and/or intermediate solid solutions (solidsolutions between a terminal solid solution and/or element). As anonlimiting example, some terminal solid solutions are not brittleenough to be milled for size reduction. Other embodiments may be toohard to be milled. The use of inter-metallic materials and/orintermediate solid solutions can address some of these drawbacks.

The advantages of particles 1502 having an inter-metallic phase aremulti-fold. As a nonlimiting example, a precursor material suitable foruse in a thin film solar cell may contain group IB and group IIIAelements such as copper and indium, respectively. If an inter-metallicphase of Cu—In is used such as Cu₁In₂, then Indium is part of an In-richCu material and not added as pure indium. Adding pure indium as ametallic particle is challenging due to the difficulty in achieving Inparticle synthesis with high yield, small and narrow nanoparticle sizedistribution, and requiring particle size discrimination, which addsfurther cost. Using inter-metallic In-rich Cu particles avoids pureelemental In as a precursor material. Additionally, because theinter-metallic material is Cu poor, this also advantageously allows Cuto be added separately to achieve precisely the amount of Cu desired inthe precursor material. The Cu is not tied to the ratio fixed in alloysor solid solutions that can be created by Cu and In. The inter-metallicmaterial and the amount of Cu can be fine tuned as desired to reach adesired stoichiometric ratio. Ball milling of these particles results inno need for particle size discrimination, which decreases cost andimproves the throughput of the material production process.

In some specific embodiments of the present invention, having aninter-metallic material provides a broader range of flexibility. Sinceeconomically manufacturing elemental indium particles is difficult, itwould be advantageous to have an indium-source that is more economicallyinteresting. Additionally, it would be advantageous if this indiumsource still allows varying both the Cu/(In+Ga) and Ga/(In+Ga) in thelayer independently of each other. As one nonlimiting example, adistinction can be made between Cu₁₁In₉ and Cu₁In₂ with aninter-metallic phase. This particularly true if only one layer ofprecursor material is used. If, for this particular example, if indiumis only provided by Cu₁₁In₉, there is more restriction whatstoichiometric ratio can be created in a final group IB-IIIA-VIAcompound. With Cu₁In₂ as the only indium source, however, there is muchgreater range of ratio can be created in a final group IB-IIIA-VIAcompound. Cu₁In₂ allows you to vary both the Cu/(In+Ga) and Ga/(In+Ga)independently in a broad range, whereas Cu11In9 does not. For instance,Cu11In9 does only allow for Ga/(In+Ga)=0.25 with Cu/(In+Ga)>0.92. Yetanother example, Cu11In9 does only allow for Ga/(In+Ga)=0.20 withCu/(In+Ga)>0.98. Yet another example, Cu11In9 does only allow forGa/(In+Ga)=0.15 with Cu/(In+Ga)>1.04. Thus for an intermetallicmaterial, particularly when the intermetallic material is a sole sourceof one of the elements in the final compound, the final compound may becreated with stoichiometric ratios that more broadly explore the boundsof Cu/(In+Ga) with a compositional range of about 0.7 to about 1.0, andGa/(In+Ga) with a compositional range of about 0.05 to about 0.3. Inother embodiments, Cu/(In+Ga) compositional range may be about 0.01 toabout 1.0. In other embodiments, the Cu/(In+Ga) compositional range maybe about 0.01 to about 1.1. In other embodiments, the Cu/(In+Ga)compositional range may be about 0.01 to about 1.5. This typicallyresults in additional Cu_(x)Se_(y) which we might be able to removeafterwards if it is at the top surface. It should be understood thatthese ratios may apply to any of the above embodiments described herein.

Furthermore, it should be understood that during processing, anintermetallic material may create more liquid than other compounds. As anonlimiting example, Cu₁In₂ will form more liquid when heated duringprocessing than Cu11In9. More liquid promotes more atomic intermixingsince it easier for material to move and mix while in a liquid stage.

Additionally, there are specific advantages for particular types ofinter-metallic particles such as, but not limited to, Cu₁In₂. Cu₁In₂ isa material that is metastable. The material is more prone todecomposition, which advantageously for the present invention, willincrease the rate of reaction (kinetically). Further, the material isless prone to oxidation (e.g. compared to pure In) and this furthersimplifies processing. This material may also be single-phase, whichwould make it more uniform as a precursor material, resulting in betteryield.

As seen in FIGS. 18 and 19, after the layer 1500 is deposited over thesubstrate 1506, it may then be heated in a suitable atmosphere to reactthe layer 1500 in FIG. 18 and form film 1510 shown in FIG. 19. It shouldbe understood that the layer 1500 may be used in conjunction with layers915 and 917 as described above with regards to FIGS. 13A-13B. The layer915 may be comprised of various materials including but not limited atleast one of the following: a group IB element, a group IIIA element, agroup VIA element, a group IA element (new style: group 1), a binaryand/or multinary alloy of any of the preceding elements, a solidsolution of any of the preceding elements. It should be understood thatsodium or a sodium-based material such as but not limited to sodium, asodium compound, sodium fluoride, and/or sodium indium sulfide, may alsobe used in layer 915 with the precursor material to improve thequalities of the resulting film. FIG. 19 shows that a layer 932 may alsobe used as described with regards to FIG. 13F. Any of the methodsuggested previously with regards to sodium content may also be adaptedfor use with the embodiments shown in FIGS. 17-19.

It should be understood that other embodiments of the present inventionalso disclose material comprised of at least two elements wherein theamount of at least one element in the material is less than about 50molar percent of the total molar amount of that element in the precursormaterial. This includes embodiments where the amount of group IB elementis less than the amount of group IIIA element in inter-metallicmaterial. As a nonlimiting example, this may include other group IBpoor, group IB-IIIA materials such as Cu-poor Cu_(x)In_(y) particles(where x<y). The amount of group IIIA material may be in any range asdesired (more than about 50 molar percent of the element in theprecursor material or less than 50 molar percent). In anothernonlimiting example, Cu₁Ga₂ may be used with elemental Cu and elementalIn. Although this material is not an inter-metallic material, thismaterial is a intermediate solid solution and is different from aterminal solid solution. All solid particles are created based on aCu₁Ga₂ precursor. In this embodiment, no emulsions are used.

In still other embodiments of the present invention, other viableprecursor materials may be formed using a group IB rich, group IB-IIIAmaterial. As a nonlimiting example, a variety of intermediatesolid-solutions may be used. Cu—Ga (38 at % Ga) may be used in precursorlayer 1500 with elemental indium and elemental copper. In yet anotherembodiment, Cu—Ga (30 at % Ga) may be used in precursor layer 1500 withelemental copper and elemental indium. Both of these embodimentsdescribe Cu-rich materials with the Group IIIA element being less thanabout 50 molar percent of that element in the precursor material. Instill further embodiments, Cu—Ga (multiphasic, 25 at % Ga) may be usedwith elemental copper and indium to form the desired precursor layer. Itshould be understood that nanoparticles of these materials may becreated by mechanical milling or other size reduction methods. In otherembodiments, these particles may be made by electroexplosive wire (EEW)processing, evaporation condensation (EC), pulsed plasma processing, orother methods. Although not limited to the following, the particlessizes may be in the range of about 10 nm to about 1 micron. They may beof any shape as described herein.

Referring now to FIG. 20, in a still further embodiment of the presentinvention, two or more layers of materials may be coated, printed, orotherwise formed to provide a precursor layer with the desiredstoichiometric ratio. As a nonlimiting example, layer 1530 may contain aprecursor material having Cu₁₁In₉ and a Ga source such as elemental Gaand/or Ga_(x)Se_(y). A copper rich precursor layer 1532 containingCu₇₈In₂₈ (solid-solution) and elemental indium or In_(x)Se_(y) may beprinted over layer 1530. In such an embodiment, the resulting overallratios may have Cu/(In+Ga)=0.85 and Ga/(In+Ga) 0.19. In one embodimentof the resulting film, the film may have a stoichiometric ratio ofCu/(In+Ga) with a compositional range of about 0.7 to about 1.0 andGa/(In+Ga) with a compositional range of about 0.05 to about 0.3.

Referring now to FIG. 21, it should be understood that in someembodiments of the present invention, the inter-metallic material isused as a feedstock or starting material from which particles and/ornanoparticles may be formed. As a nonlimiting example, FIG. 21 shows oneinter-metallic feedstock particle 1550 being processed to form otherparticles. Any method used for size reduction and/or shape change may besuitable including but not limited to milling, EEW, EC, pulsed plasmaprocessing, or combinations thereof. Particles 552, 554, 556, and 558may be formed. These particles may be of varying shapes and some maycontain only the inter-metallic phase while others may contain thatphase and other material phases.

Referring now to FIGS. 22A and 22B, flakes 1600 (microflakes and/ornanoflakes) provide certain advantages over other non-spherical shapessuch as but not limited to platelets. The flakes 1600 provide for highlyefficient stacking (due to substantially uniform thickness in Z-axis)and high surface area (in X and Y axes). This leads to faster reactions,better kinetics, and more uniform products/films/compounds (with fewerside propagations). Platelet 1602 as seen in FIGS. 23A and 23B fail tohave all of the above advantages.

Coating Stabilization

Referring now to FIGS. 24A-24E, it should be understood that it may bedesirable in some embodiments to essentially lock in the position ofindividual nanoparticles or groups of nanoparticles in a coating ofnanoparticles. In the context of CIGS solar cells made by solutiondeposition of nanoparticles of metallic precursors, this locking in ofnanoparticle position is of particular interest. This embodiment of thepresent invention makes use of dispersants that can react with itself orcross-link to effectively lock in a matrix of nanoparticles with thinorganic layer between them. Upon heating, the organic or substantiallyorganic material burns out just before or during the CIGS layer isformed. Although not limited to the following, some suitable materialsmay include one or more of the following:

1. metallic stearates, subsequently crosslinked by electron beam ororganic peroxide;

2. metallic salts of unsaturated fatty acids, subsequently crosslinkedby free radical polymerization of the vinyl groups, initiated by organicperoxide or other free radical initiator;

3. unsaturated fatty acids, subsequently crosslinked by free radicalpolymerization of the vinyl groups, initiated by organic peroxide orother free radical initiator;

4. unsaturated fatty alcohols, subsequently crosslinked by free radicalpolymerization of the vinyl groups, initiated by organic peroxide orother free radical initiator;

5. unsaturated fatty amides, such as dehydrodenated derivatives ofoleamides and erucamides, and bis-stearamides, subsequently crosslinkedby free radical polymerization of the vinyl groups, initiated by organicperoxide or other free radical initiator;

6. unsaturated fatty thiols, subsequently crosslinked by free radicalpolymerization of the vinyl groups, initiated by organic peroxide orother free radical initiator;

7. saturated fatty thiols, without subsequent reaction required due toextraordinary thiol affinity to metallic nanoparticles as well asnanocrystallinity of the saturated fatty layer;

8. waxes, low molecular weight (MW) polyolefins, partially oxidizedwaxes, partially oxidized low MW polyolefins, paraffinic waxes,microcrystalline waxes, carnauba wax, vegetable oils and animal fats(saturated, unsaturated, and polyunsaturated), glycerol monostearate;

9. unsaturated fatty sulfonates, subsequently crosslinked by freeradical polymerization of the vinyl groups, initiated by organicperoxide or other free radical initiator;

10. saturated fatty sulfonates, subsequently crosslinked by electronbeam or organic peroxide;

11. unsaturated fatty phosphonates, subsequently crosslinked by freeradical polymerization of the vinyl groups, initiated by organicperoxide or other free radical initiator;

12. saturated fatty phosphonates, subsequently crosslinked by electronbeam or organic peroxide;

13. nitrilotrismethylene phosphonic acid (NTMP), without subsequentreaction required due to extraordinary NTMP affinity to metallicnanoparticles;

14. epoxy, low MW, subsequently thermally crosslinked;

15. phenol/resorcinol formaldehyde novolac polymer, low MW, subsequentlythermally crosslinked;

16. urea formaldehyde, subsequently thermally crosslinked;

17. resorcinol and epoxy, low MW, subsequently thermally crosslinked;

18. melamine formaldehyde, subsequently thermally crosslinked;

19. polysulfide, low MW), without subsequent reaction required due toextraordinary polysulfide affinity to metallic nanoparticles;

20. cyanoacrylate, low MW, subsequently or simultaneously crosslinked bytraces of water either on the nanoparticle or in the surrounding matrix;

21. unsaturated polyester, low MW subsequently thermally crosslinked;

22. polyimide, low MW subsequently thermally crosslinked;

23. polybenzimidazole, low MW subsequently thermally crosslinked;

24. UV-curable acrylics and modified acrylics;

25. UV-curable epoxies;

The above materials are available for various sources including but notlimited to Abril Industrial Waxes Ltd., AlliedSignal Inc., Specialty Waxand Additives, or Clariant (www.clariant.com) Sulzbach, Germany.

FIG. 24A shows one embodiment of the present invention. The embodimentof FIG. 24A shows one type of nanoparticle 1200 which may be a binaryalloy nanoparticle such as a group IB-VIA particle, a group IIIA-VIAparticle, or a group IB-IIIA particle. Another type of nanoparticle 1202may be included in the mixture. This particle may be an elementalnanoparticle or an alloy nanoparticle such as but not limited to thebinary alloy nanoparticles previously described. As seen in FIG. 24A,the particles are coated with a layer of material 1204 corresponding tothe organic material that will lock the particles in a matrix. Thematerial 1204 may be applied to the particles 1200 and/or 1202 before,during, or after deposition of the particles on to the substrate 1206.Although the particles are shown to be spherical, the use of sphericalparticles is purely exemplary. It should be understood that flakesand/or other shaped particles may be used with or without sphericalparticles using the techniques described in FIGS. 24A-24E.

FIG. 24B shows that a layer 1210 of group IIIA or VIA material may beadded on top of particles 1200 and 1202. By way of example and notlimitation, this may be a layer of selenium or sulfur to increase theamount of group VIA material in the precursor layer of nanoparticles. Insome embodiments, this layer may be a layer of gallium or gallium alloyto create the desired bandgap grading with higher concentrations ofgallium near the surface of the absorber layer.

FIG. 24C shows that in this embodiment, heating of the material in layer1210 will cause it to migrate between the nanoparticles 1200 and 1202.In one embodiment of the present invention, the precursor layer may bebetween about 4.0 to about 0.5 microns thick. The layer containingparticles may have a thickness in the range of about 4.0 microns toabout 0.5 microns. The particles in the layer may be between about 1nanometer and about 25 microns in size, preferably between about 25nanometers and about 300 nanometers in size. It is noted that theparticles may be initially larger than the final thickness of theIB-IIIA-VIA compound film. The particles may be mixed with solvents,carriers, dispersants etc. to prepare an ink or a paste that is suitablefor wet deposition over the precursor layer to form the layer. It isalso noted that the heating of the layer of particles may be carried outby an RTA process, e.g., as described above.

FIG. 24D shows that further heating causes the nanoparticle 1200, 1202,and the material from layer 1210 to react and form the desired groupIB-IIIA-VIA semiconductor 1212. Processing comprises annealing with aramp-rate of 1-5° C./sec, preferably over 5° C./sec, to a temperature ofabout 225 to 550° C. Optionally, processing comprises annealing with aramp-rate of 1-5° C./sec, preferably over 5° C./sec, to a temperature ofabout 225 to 550° C. preferably for about 30 seconds to about 600seconds to enhance conversion of indium hydroxide or other hydroxide,densification and/or alloying between Cu, In, and Ga in an atmospherecontaining hydrogen gas, where the plateau temperature not necessarilyis kept constant in time. Optionally, processing further compriseselenizing this annealed layer with a ramp-rate of 1-5 C/sec, preferablyover 5 C/sec, to a temperature of about 225 to 575 C for a time periodof about 60 seconds to about 10 minutes in Se vapor, where the plateautemperature not necessarily is kept constant in time, to form thethin-film containing one or more chalcogenide compounds containing Cu,In, Ga, and Se. Optionally, processing comprise selenizing without theseparate annealing step in an atmosphere containing hydrogen gas, butmay be densified and selenized in one step with a ramp-rate of 1-5C/sec, preferably over 5 C/sec, to a temperature of 225 to 575 C for atime period of about 120 seconds to about 20 minutes in an atmospherecontaining either H2Se or a mixture of H2 and Se vapor.

FIG. 24E shows another embodiment wherein the precursor layer maycomprise of three types of particles 1200, 1202, and 1220. The particles1220 may contain the material that was previously incorporated in layer1210. Optionally, a fourth type of particle 1222 may also be included.This may be heated to arrive at semiconductor layer 1212.

Advantageously, using the organic material allows the annealing step toreach greater than 350 degree without the danger of forming intermediatephases along the way to getting to the desired temperature.

Advantageously, using the material 1204 prevents indium, selenium, andor gallium liquid from migrating away from the desired regions beforethe CIGS formation temperature has been achieved (i.e. special andtemperoal homogeneity preserved).

Advantageously, using the o material 1204 prevents loss of nanoparticlesfrom film between processing steps before selenization. This maybeparticular useful in manufacturing especially if subsrate will be rolledup and/or move quickly through process.

Advantageously, using the material 1204 allows the use fo galliumnanoparticles without worryigna bout being a liquid at room temperature.

Advantageously, using the material 1204 prevents the nanoparticle forpremature reaction/oxidation. This allows particles to react much morereadily.

While the invention has been described and illustrated with reference tocertain particular embodiments thereof, those skilled in the art willappreciate that various adaptations, changes, modifications,substitutions, deletions, or additions of procedures and protocols maybe made without departing from the spirit and scope of the invention.For example, with any of the above embodiments, microflakes may bereplaced by and/or mixed with nanoflakes wherein the lengths of theplanar nanoflakes are about 500 nm to about 1 nm. As a nonlimitingexample, the nanoflakes may have lengths and/or largest lateraldimension of about 300 nm to about 10 nm. In other embodiments, thenanoflakes may be of thickness in the range of about 200 nm to about 20nm. In another embodiment, these nanoflakes may be of thickness in therange of about 100 nm to about 10 nm. In one embodiment, thesenanoflakes may be of thickness in the range of about 200 nm to about 20nm. As mentioned, some embodiments of the invention may include bothmicroflakes and nanoflakes. Other may include flakes that areexclusively in the size range of microflakes or the size range ofnanoflakes. With any of the above embodiments, the microflakes may bereplaced and/or combined with microrods which are substantially linear,elongate members. Still further embodiments may combine nanorods withmicroflakes in the precursor layer. The microrods may have lengthsbetween about 500 nm to about 1 nm. In another embodiment, the nanorodsmay have lengths between about 500 nm and 20 nm. In yet anotherembodiment, the nanorods may have lengths between about 300 nm and 30nm. Any of the above embodiments may be used on rigid substrate,flexible substrate, or a combinations of the two such as but not limitedto a flexible substrate that become rigid during processing due to itsmaterial properties. In one embodiment of the present invention, theparticles may be plates and/or discs and/or flakes and/or wires and/orrods of micro-sized proportions. In another embodiment of the presentinvention, the particles may be nanoplates and/or nanodiscs and/ornanoflakes and/or nanowires and/or nanorods of nano-sized proportions.Again, any of the foregoing may also be combined with sphericalparticles in a suspension. Some embodiments may have all sphericalparticles, all non-spherical particles, and/or mixtures of particles ofvarious shapes. It should be understood that the solid group IIIA-basedparticles may be used in single or multiple combination with particlesof other shapes and/or composition. This may include shapes such as butnot limited to spherical, planar, flake, platelet, other non-spherical,and/or single or multiple combinations of the foregoing. As formaterials, this may include alloys, elementals, chalcogenides,inter-metallics, solid-solutions and/or single or multiple combinationsof the foregoing in any shape or form. Use of solid particles withdispersions and/or emulsions of the foregoing is also envisioned. Thesolid solutions are described in pending U.S. patent application Ser.No. 10/474,259 and published as US20040219730, fully incorporated hereinby reference for all purposes. The following applications are also fullyincorporated herein by reference: Ser. No. 11/395,438, Ser. No.11/395,668, and Ser. No. 11/395,426 both filed Mar. 30, 2006. Any of theembodiments described in those applications may be adapted for use withthe particles described herein.

For any of the above embodiments, it should be understood that inaddition to the aforementioned, the temperature used during annealingmay also vary over different time periods of precursor layer processing.As a nonlimiting example, the heating may occur at a first temperatureover an initial processing time period and proceed to other temperaturesfor subsequent time periods of the processing. Optionally, the methodmay include intentionally creating one or more temperature dips so that,as a nonlimiting example, the method comprises heating, cooling,heating, and subsequent cooling. Some embodiments may use a two-stepabsorber growth (non-reactive anneal for densification followed byreactive anneal) without cool-down and ramp-up between densification andselenization/sulfurization. Various heating methods, including notheating the substrate, but only the precursor layer (laser) may be used.Others heating techniques may use muffle heating, convection heating,IR-heating. Some embodiments may use the same or different techniquesfor heating the top surface and bottomw surface of the substrate.Basically, all heating mechanisms, being conduction, convection, andradiation may be used. All temperature gradients within the web (acrossthe thickness), being uniformly heated from bottom to top, and/orheating with a huge temperature gradient from bottom (low T) to top(high T), e.g. with a laser, and covering all web transport mechanismsthrough the furnace (including but not limited to being free-spanthrough the module, dragging over a dense or partially open surface, orrelying on a belt), orientation of the furnace, horizontally,vertically, or anything in between.

For any of the above embodiments, it is also possible to have two ormore elements of IB elements in the chalcogenide particle and/or theresulting film. Although the description herein uses an ink, it shouldbe understood that in some embodiments, the ink may have the consistencyof a paste or slurry. Additionally, concentrations, amounts, and othernumerical data may be presented herein in a range format. It is to beunderstood that such range format is used merely for convenience andbrevity and should be interpreted flexibly to include not only thenumerical values explicitly recited as the limits of the range, but alsoto include all the individual numerical values or sub-ranges encompassedwithin that range as if each numerical value and sub-range is explicitlyrecited. For example, a size range of about 1 nm to about 200 nm shouldbe interpreted to include not only the explicitly recited limits ofabout 1 nm and about 200 nm, but also to include individual sizes suchas 2 nm, 3 nm, 4 nm, and sub-ranges such as 10 nm to 50 nm, 20 nm to 100nm, etc. . . .

For example, still other embodiments of the present invention may use aCu—In precursor material wherein Cu—In contribute less than about 50percent of both Cu and In found in the precursor material. The remainingamount is incorporated by elemental form or by non IB-IIIA alloys. Thus,a Cu₁₁In₉ may be used with elemental Cu, In, and Ga to form a resultingfilm. In another embodiment, instead of elemental Cu, In, and Ga, othermaterials such as Cu—Se, In—Se, and/or Ga—Se may be substituted assource of the group IB or IIIA material. Optionally, in otherembodiment, the IB source may be any particle that contains Cu withoutbeing alloyed with In and Ga (Cu, Cu—Se). The IIIA source may be anyparticle that contains In without Cu (In—Se, In—Ga—Se) or any particlethat contains Ga without Cu (Ga, Ga—Se, or In—Ga—Se). Other embodimentsmay have these combinations of the IB material in a nitride or oxideform. Still other embodiments may have these combinations of the IIIAmaterial in a nitride or oxide form. The present invention may use anycombination of elements and/or selenides (binary, ternary, or multinary)may be used. Optionally, some other embodiments may use oxides such asIn₂O₃ to add the desired amounts of materials. It should be understoodfor any of the above embodiments that more than one solid solution maybe used, multi-phasic alloys, and/or more general alloys may also beused. For any of the above embodiments, the annealing process may alsoinvolve exposure of the compound film to a gas such as H₂, CO, N₂, Ar,H₂Se, or Se vapor, S vapor, or other group VIA containing vapor. Theremay be a two stage process where there is an initial anneal in a nongroup-VIA based atmosphere and then a second or more heating in groupVIA-based atmosphere. There may be a two stage process where there is aninitial anneal in a non group-VIA based atmosphere and then a secondheating in a non-group VIA based atmosphere, wherein VIA material isplaced directly on the stack for the second heating and additional isthe VIA-containing vapor is not used. Alternatively, some may use a onestage process to create a final film, or a multi-stage process whereeach heating step use a different atmospher.

It should also be understood that several intermediate solid solutionsmay also be suitable for use according to the present invention. Asnonlimiting examples, a composition in the δ phase for Cu—In (about42.52 to about 44.3 wt % In) and/or a composition between the δ phasefor Cu—In and Cu₁₆In₉ may be suitable inter-metallic materials for usewith the present invention to form a group IB-IIIA-VIA compound. Itshould be understood that these inter-metallic materials may be mixedwith elemental or other materials such as Cu—Se, In—Se, and/or Ga—Se toprovide sources of the group IB or IIIA material to reach the desiredstoichiometric ratios in the final compound. Other nonlimiting examplesof inter-metallic material include compositions of Cu—Ga containing thefollowing phases: γ₁ (about 31.8 to about 39.8 wt % Ga), γ₂ (about 36.0to about 39.9 wt % Ga), γ₃ (about 39.7 to about −44.9 wt % Ga), thephase between γ₂ and γ₃, the phase between the terminal solid solutionand γ₁, and θ (about 66.7 to about 68.7 wt % Ga). For Cu—Ga, a suitablecomposition is also found in the range in between the terminalsolid-solution of and the intermediate solid-solution next to it.Advantageously, some of these inter-metallic materials may bemulti-phasic which are more likely to lead to brittle materials that canbe mechanically milled. Phase diagrams for the following materials maybe found in ASM Handbook, Volume 3 Alloy Phase Diagrams (1992) by ASMInternational and fully incorporated herein by reference for allpurposes. Some specific examples (fully incorporated herein byreference) may be found on pages 2-168, 2-170, 2-176, 2-178, 2-208,2-214, 2-257, and/or 2-259. It should also be understood that a particlemay have portions that are of a solid alloy and portions that are phaseseparated into individual elements or other alloys that are liquid.

It should be understood that any of the embodiments herein may beadapted for use in a one step process, or a two step process, or amulti-step process for forming a photovoltaic absorber layer. One stepprocesses do not require a second follow-up process to convert the filminto an absorber layer. A two step process typically creates a film thatuses a second process to convert the film into an absorber layer.Additionally, some embodiments may have anywhere from about 0 to about 5wt % oxygen in the shell.

It should be understood that the particles as described herein may beused with solids, solid solutions, intermetallics, nanoglobules,emulsions, nanoglobule, emulsion, or other types of particles. It shouldalso be understood that prior to deposition of any material on thesubstrate, the metal foil may undergo conditioning (cleaning,smoothening, and possible surface treatment for subsequent steps), suchas but not limited to corona cleaning, wet chemical cleaning, plasmacleaning, ultrasmooth re-rolling, electro-polishing, and/or CMP slurrypolishing.

It should be understood that the deposition methods for use withdepositing precursor material(s) may include one or more of thefollowing: solution-deposition of particulates, like coating, printing,and spraying, sol-gel, electro(less) deposition (HBP, CBD, e-Dep),precipitations, (chemical) vapor deposition, sputtering, evaporation,ion plating, extrusion, cladding, thermal spray, where several of thesemethods can be plasma-enhanced) and precursor/film-conversion methods,where the latter can be either chemically, physically, and/ormechanically, and covers both partial and complete changes of theprecursor/film and/or surface only.

The publications discussed or cited herein are provided solely for theirdisclosure prior to the filing date of the present application. Nothingherein is to be construed as an admission that the present invention isnot entitled to antedate such publication by virtue of prior invention.Further, the dates of publication provided may be different from theactual publication dates which may need to be independently confirmed.All publications mentioned herein are incorporated herein by referenceto disclose and describe the structures and/or methods in connectionwith which the publications are cited. The following applications arealso incorporated herein by reference for all purposes: U.S. patentapplication Ser. No. 11/290,633 entitled “CHALCOGENIDE SOLAR CELLS”filed Nov. 29, 2005, U.S. patent application Ser. No. 10/782,017,entitled “SOLUTION-BASED FABRICATION OF PHOTOVOLTAIC CELL” filed Feb.19, 2004, U.S. patent application Ser. No. 10/943,657, entitled “COATEDNANOPARTICLES AND QUANTUM DOTS FOR SOLUTION-BASED FABRICATION OFPHOTOVOLTAIC CELLS” filed Sep. 18, 2004, U.S. patent application Ser.No. 11/081,163, entitled “METALLIC DISPERSION”, filed Mar. 16, 2005, andU.S. patent application Ser. No. 10/943,685, entitled “FORMATION OF CIGSABSORBER LAYERS ON FOIL SUBSTRATES”, filed Sep. 18, 2004, Ser. No.11/361,498 entitled “HIGH-THROUGHPUT PRINTING OF SEMICONDUCTOR PRECURSORLAYER FROM MICROFLAKE PARTICLES” filed Feb. 23, 2006, Ser. No.11/395,426 filed Mar. 30, 2006, the entire disclosures of which areincorporated herein by reference.

While the above is a complete description of the preferred embodiment ofthe present invention, it is possible to use various alternatives,modifications and equivalents. Therefore, the scope of the presentinvention should be determined not with reference to the abovedescription but should, instead, be determined with reference to theappended claims, along with their full scope of equivalents. Anyfeature, whether preferred or not, may be combined with any otherfeature, whether preferred or not. In the claims that follow, theindefinite article “A”, or “An” refers to a quantity of one or more ofthe item following the article, except where expressly stated otherwise.The appended claims are not to be interpreted as includingmeans-plus-function limitations, unless such a limitation is explicitlyrecited in a given claim using the phrase “means for.”

1. A method comprising: formulating an ink of particles wherein about50% or more of all the particles are microflakes each containing atleast one element from group IB, IIIA and/or VIA and having anon-spherical, planar shape with irregular, jagged circumferentialoutline, wherein overall amounts of elements from group IB, IIIA and/orVIA contained in the ink are such that the ink has a desiredstoichiometric ratio of the elements; coating a substrate with the inkto form a precursor layer; and processing the precursor layer in asuitable atmosphere to form a dense film; wherein at least one set ofthe particles in the ink are inter-metallic microflake particlescontaining at least one group IB-IIIA inter-metallic alloy phase;wherein liquid group IIIA material is included in the ink.
 2. The methodof claim 1 wherein the dense film is used in the formation of asemiconductor absorber for a photovoltaic device.
 3. The method of claim1 wherein substantially all of the particles have a non-spherical,planar shape.
 4. The method of claim 1 wherein the particles comprise ofmicroflakes and nanoflakes.
 5. The method of claim 1 wherein at leastabout 75% or more of a total weight of all the particles aremicroflakes.
 6. The method of claim 2 wherein the planar shape of themicroflakes results in grain sizes of at least about 2.0 μm in at leastone dimension in the semiconductor absorber of a photovoltaic device. 7.The method of claim 2 wherein the planar shape of the microflakesresults in grain sizes of at least about 1.0 μm in at least onedimension in the semiconductor absorber of a photovoltaic device.
 8. Themethod of claim 2 wherein the planar shape of the microflakes results ingrain sizes of at least about 0.5 μm in at least one dimension in thesemiconductor absorber of a photovoltaic device.
 9. The method of claim1 wherein the microflakes are of random planar shape and/or a randomsize distribution.
 10. A method comprising: formulating an ink ofparticles wherein about 50% or more of all the particles are microflakeseach containing at least one element from group IB, IIIA and/or VIA andhaving a non-spherical, planar shape, wherein overall amounts ofelements from group IB, IIIA and/or VIA contained in the ink are suchthat the ink has a desired stoichiometric ratio of the elements; coatinga substrate with the ink to form a precursor layer; and processing theprecursor layer in a suitable atmosphere to form a dense film; whereinat least one set of the particles in the ink are inter-metallicmicroflake particles containing at least one group IB-IIIAinter-metallic alloy phase; wherein liquid group IIIA material isincluded in the ink.
 11. A method comprising: formulating an ink ofparticles wherein about 50% or more of all the particles are microflakeseach containing at least one element from group IB, IIIA and/or VIA andhaving a non-spherical, planar shape with an irregular circumferentialoutline, wherein overall amounts of elements from group IB, IIIA and/orVIA contained in the ink are such that the ink has a desiredstoichiometric ratio of the elements; coating a substrate with the inkto form a precursor layer; processing the precursor layer in a suitableatmosphere to form a dense film; wherein at least one set of theparticles in the ink are inter-metallic microflake particles containingat least one group IB-IIIA inter-metallic alloy phase; wherein liquidgroup IIIA material is included in the ink.
 12. The method of claim 10wherein the dense film is used in the formation of a semiconductorabsorber for a photovoltaic device.
 13. The method of claim 10 whereinsubstantially all of the particles have a non-spherical, planar shape.14. The method of claim 10 wherein the particles comprise of microflakesand nanoflakes.
 15. The method of claim 10 wherein at least about 75% ormore of a total weight of all the particles are microflakes.
 16. Themethod of claim 12 wherein the planar shape of the microflakes resultsin grain sizes of at least about 2.0 μm in at least one dimension in thesemiconductor absorber of a photovoltaic device.
 17. The method of claim12 wherein the planar shape of the microflakes results in grain sizes ofat least about 1.0 μm in at least one dimension in the semiconductorabsorber of a photovoltaic device.
 18. The method of claim 12 whereinthe planar shape of the microflakes results in grain sizes of at leastabout 0.5 μm in at least one dimension in the semiconductor absorber ofa photovoltaic device.
 19. The method of claim 12 wherein themicroflakes are of random planar shape and/or a random sizedistribution.